National Library of Energy BETA

Sample records for transfer electronic transmission

  1. Electron Transfer

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    3 Pierre Kennepohl1,2 and Edward Solomon1* 1Department of Chemistry, Stanford University, Stanford, CA 94305 Electron transfer, or the act of moving an electron from one place to another, is amongst the simplest of chemical processes, yet certainly one of the most critical. The process of efficiently and controllably moving electrons around is one of the primary regulation mechanisms in biology. Without stringent control of electrons in living organisms, life could simply not exist. For example,

  2. Ponderomotive phase plate for transmission electron microscopes...

    Office of Scientific and Technical Information (OSTI)

    A ponderomotive phase plate system and method for controllably producing highly tunable phase contrast transfer functions in a transmission electron microscope (TEM) for high ...

  3. Dynamic Transmission Electron Microscopy

    SciTech Connect (OSTI)

    Evans, James E.; Jungjohann, K. L.; Browning, Nigel D.

    2012-10-12

    Dynamic transmission electron microscopy (DTEM) combines the benefits of high spatial resolution electron microscopy with the high temporal resolution of ultrafast lasers. The incorporation of these two components into a single instrument provides a perfect platform for in situ observations of material processes. However, previous DTEM applications have focused on observing structural changes occurring in samples exposed to high vacuum. Therefore, in order to expand the pump-probe experimental regime to more natural environmental conditions, in situ gas and liquid chambers must be coupled with Dynamic TEM. This chapter describes the current and future applications of in situ liquid DTEM to permit time-resolved atomic scale observations in an aqueous environment, Although this chapter focuses mostly on in situ liquid imaging, the same research potential exists for in situ gas experiments and the successful integration of these techniques promises new insights for understanding nanoparticle, catalyst and biological protein dynamics with unprecedented spatiotemporal resolution.

  4. Ponderomotive phase plate for transmission electron microscopes

    DOE Patents [OSTI]

    Reed, Bryan W. (Livermore, CA)

    2012-07-10

    A ponderomotive phase plate system and method for controllably producing highly tunable phase contrast transfer functions in a transmission electron microscope (TEM) for high resolution and biological phase contrast imaging. The system and method includes a laser source and a beam transport system to produce a focused laser crossover as a phase plate, so that a ponderomotive potential of the focused laser crossover produces a scattering-angle-dependent phase shift in the electrons of the post-sample electron beam corresponding to a desired phase contrast transfer function.

  5. Scientific Achievement Analytical Transmission Electron Microscopy

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Analytical Transmission Electron Microscopy (TEM) method was developed to determine thickness and wrinkles in electron beam sensitive 2-dimensional (2D) MFI nanosheets....

  6. Transmission electron microscope CCD camera

    DOE Patents [OSTI]

    Downing, Kenneth H.

    1999-01-01

    In order to improve the performance of a CCD camera on a high voltage electron microscope, an electron decelerator is inserted between the microscope column and the CCD. This arrangement optimizes the interaction of the electron beam with the scintillator of the CCD camera while retaining optimization of the microscope optics and of the interaction of the beam with the specimen. Changing the electron beam energy between the specimen and camera allows both to be optimized.

  7. In Situ Transmission Electron Microscopy. (Conference) | SciTech...

    Office of Scientific and Technical Information (OSTI)

    In Situ Transmission Electron Microscopy. Citation Details In-Document Search Title: In Situ Transmission Electron Microscopy. Abstract not provided. Authors: Jungjohann, Katherine ...

  8. Electronic Coupling Dependence of Ultrafast Interfacial Electron Transfer

    Office of Scientific and Technical Information (OSTI)

    on Nanocrystalline Thin Films and Single Crystal (Technical Report) | SciTech Connect Electronic Coupling Dependence of Ultrafast Interfacial Electron Transfer on Nanocrystalline Thin Films and Single Crystal Citation Details In-Document Search Title: Electronic Coupling Dependence of Ultrafast Interfacial Electron Transfer on Nanocrystalline Thin Films and Single Crystal The long-term goal of the proposed research is to understand electron transfer dynamics in nanoparticle/liquid interface.

  9. Photo-induced electron transfer method

    DOE Patents [OSTI]

    Wohlgemuth, Roland; Calvin, Melvin

    1984-01-01

    The efficiency of photo-induced electron transfer reactions is increased and the back transfer of electrons in such reactions is greatly reduced when a photo-sensitizer zinc porphyrin-surfactant and an electron donor manganese porphyrin-surfactant are admixed into phospho-lipid membranes. The phospholipids comprising said membranes are selected from phospholipids whose head portions are negatively charged. Said membranes are contacted with an aqueous medium in which an essentially neutral viologen electron acceptor is admixed. Catalysts capable of transfering electrons from reduced viologen electron acceptor to hydrogen to produce elemental hydrogen are also included in the aqueous medium. An oxidizable olefin is also admixed in the phospholipid for the purpose of combining with oxygen that coordinates with oxidized electron donor manganese porphyrin-surfactant.

  10. Photo-induced electron transfer method

    DOE Patents [OSTI]

    Wohlgemuth, R.; Calvin, M.

    1984-01-24

    The efficiency of photo-induced electron transfer reactions is increased and the back transfer of electrons in such reactions is greatly reduced when a photo-sensitizer zinc porphyrin-surfactant and an electron donor manganese porphyrin-surfactant are admixed into phospholipid membranes. The phospholipids comprising said membranes are selected from phospholipids whose head portions are negatively charged. Said membranes are contacted with an aqueous medium in which an essentially neutral viologen electron acceptor is admixed. Catalysts capable of transferring electrons from reduced viologen electron acceptor to hydrogen to produce elemental hydrogen are also included in the aqueous medium. An oxidizable olefin is also admixed in the phospholipid for the purpose of combining with oxygen that coordinates with oxidized electron donor manganese porphyrin-surfactant.

  11. In situ transmission electron microscopy investigation of the...

    Office of Scientific and Technical Information (OSTI)

    In situ transmission electron microscopy investigation of the interfacial reaction between Ni and Al during rapid heating in a nanocalorimeter Grapes, Michael D. Department of...

  12. In situ transmission electron microscopy investigation of the...

    Office of Scientific and Technical Information (OSTI)

    Published Article: In situ transmission electron microscopy investigation of the interfacial reaction between Ni and Al during rapid heating in a nanocalorimeter Title: In situ...

  13. A Sealed Liquid Cell for In Situ Transmission Electron Microscopy...

    Office of Scientific and Technical Information (OSTI)

    A Sealed Liquid Cell for In Situ Transmission Electron Microscopy of Controlled Electrochemical Processes Citation Details In-Document Search Title: A Sealed Liquid Cell for In ...

  14. Scanning Transmission Electron Microscopy Investigations of Complex Oxides

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    | Stanford Synchrotron Radiation Lightsource Scanning Transmission Electron Microscopy Investigations of Complex Oxides Monday, May 23, 2011 - 3:30pm SSRL Conference room 137-322 Professor Tom Vogt, NanoCenter & Department of Chemistry, University of South Carolina High-Angle-Annular-Dark-Field/Scanning Transmission Electron Microscopy (HAADF/STEM) is a technique uniquely suited for detailed studies of the structure and composition of complex oxides. The HAADF detector collects electrons

  15. Reaction coordinates for electron transfer reactions

    SciTech Connect (OSTI)

    Rasaiah, Jayendran C.; Zhu Jianjun

    2008-12-07

    The polarization fluctuation and energy gap formulations of the reaction coordinate for outer sphere electron transfer are linearly related to the constant energy constraint Lagrangian multiplier m in Marcus' theory of electron transfer. The quadratic dependence of the free energies of the reactant and product intermediates on m and m+1, respectively, leads to similar dependence of the free energies on the reaction coordinates and to the same dependence of the activation energy on the reorganization energy and the standard reaction free energy. Within the approximations of a continuum model of the solvent and linear response of the longitudinal polarization to the electric field in Marcus' theory, both formulations of the reaction coordinate are expected to lead to the same results.

  16. Custody transfer enhanced by electronic billing system

    SciTech Connect (OSTI)

    Knox, R.M.

    1986-10-20

    Transcontinental Gas Pipe Line (TGPL) Corp. engineers have developed an electronic billing system for custody transfer that can reduce the cost of doing business and improve the accuracy of transfer measurements. The system accurately measures gas flow and quality, transmits gas data to a central facility, provides a capability to review the collected data, prepares bills based upon these data, and reduces staffing associated with the data collection and billing process. On-line flow computers are keys to this electronic billing system. These computers, referred to as remote terminal units (RTU's), are currently in service at TGPL at more than 30 locations with 30 more locations due to be on-line within 6 months and an additional 40 locations due within 15 months. These RTU's will be obtaining gas data from metering stations located in New York, New Jersey, Pennsylvania, Maryland, Virginia, North Carolina, Georgia, Louisiana, and Texas.

  17. Structural insights into electron transfer in caa[subscript 3...

    Office of Scientific and Technical Information (OSTI)

    Journal Article: Structural insights into electron transfer in caasubscript 3-type cytochrome oxidase Citation Details In-Document Search Title: Structural insights into electron ...

  18. Monitoring Long-Range Electron Transfer Pathways in Proteins...

    Office of Scientific and Technical Information (OSTI)

    Published Article: Monitoring Long-Range Electron Transfer Pathways in Proteins by Stimulated Attosecond Broadband X-ray Raman Spectroscopy Title: Monitoring Long-Range Electron ...

  19. Transmission Services WIST Task Force Dynamic Transfer Capability...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    ("WIST"), a Task Force of technical staff primarily from Northwest and California transmission providers and sub-regional entities, completed a report documenting Phase 1 of its...

  20. Quantum tunneling resonant electron transfer process in Lorentzian plasmas

    SciTech Connect (OSTI)

    Hong, Woo-Pyo; Jung, Young-Dae

    2014-08-15

    The quantum tunneling resonant electron transfer process between a positive ion and a neutral atom collision is investigated in nonthermal generalized Lorentzian plasmas. The result shows that the nonthermal effect enhances the resonant electron transfer cross section in Lorentzian plasmas. It is found that the nonthermal effect on the classical resonant electron transfer cross section is more significant than that on the quantum tunneling resonant charge transfer cross section. It is shown that the nonthermal effect on the resonant electron transfer cross section decreases with an increase of the Debye length. In addition, the nonthermal effect on the quantum tunneling resonant electron transfer cross section decreases with increasing collision energy. The variation of nonthermal and plasma shielding effects on the quantum tunneling resonant electron transfer process is also discussed.

  1. Studying localized corrosion using liquid cell transmission electron microscopy

    SciTech Connect (OSTI)

    Chee, See Wee; Pratt, Sarah H.; Hattar, Khalid; Duquette, David; Ross, Frances M.; Hull, Robert

    2014-11-07

    Using liquid cell transmission electron microscopy (LCTEM), localized corrosion of Cu and Al thin films immersed in aqueous NaCl solutions was studied. We demonstrate that potentiostatic control can be used to initiate pitting and that local compositional changes, due to focused ion beam implantation of Au+ ions, can modify the corrosion susceptibility of Al films. Likewise, a discussion on strategies to control the onset of pitting is also presented.

  2. Studying localized corrosion using liquid cell transmission electron microscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Chee, See Wee; Pratt, Sarah H.; Hattar, Khalid; Duquette, David; Ross, Frances M.; Hull, Robert

    2014-11-07

    Using liquid cell transmission electron microscopy (LCTEM), localized corrosion of Cu and Al thin films immersed in aqueous NaCl solutions was studied. We demonstrate that potentiostatic control can be used to initiate pitting and that local compositional changes, due to focused ion beam implantation of Au+ ions, can modify the corrosion susceptibility of Al films. Likewise, a discussion on strategies to control the onset of pitting is also presented.

  3. Concurrent in situ ion irradiation transmission electron microscope

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Hattar, K.; Bufford, D. C.; Buller, D. L.

    2014-08-29

    An in situ ion irradiation transmission electron microscope has been developed and is operational at Sandia National Laboratories. This facility permits high spatial resolution, real time observation of electron transparent samples under ion irradiation, implantation, mechanical loading, corrosive environments, and combinations thereof. This includes the simultaneous implantation of low-energy gas ions (0.8–30 keV) during high-energy heavy ion irradiation (0.8–48 MeV). In addition, initial results in polycrystalline gold foils are provided to demonstrate the range of capabilities.

  4. Photocathode Optimization for a Dynamic Transmission Electron Microscope: Final Report

    SciTech Connect (OSTI)

    Ellis, P; Flom, Z; Heinselman, K; Nguyen, T; Tung, S; Haskell, R; Reed, B W; LaGrange, T

    2011-08-04

    The Dynamic Transmission Electron Microscope (DTEM) team at Harvey Mudd College has been sponsored by LLNL to design and build a test setup for optimizing the performance of the DTEM's electron source. Unlike a traditional TEM, the DTEM achieves much faster exposure times by using photoemission from a photocathode to produce electrons for imaging. The DTEM team's work is motivated by the need to improve the coherence and current density of the electron cloud produced by the electron gun in order to increase the image resolution and contrast achievable by DTEM. The photoemission test setup is nearly complete and the team will soon complete baseline tests of electron gun performance. The photoemission laser and high voltage power supply have been repaired; the optics path for relaying the laser to the photocathode has been finalized, assembled, and aligned; the internal setup of the vacuum chamber has been finalized and mostly implemented; and system control, synchronization, and data acquisition has been implemented in LabVIEW. Immediate future work includes determining a consistent alignment procedure to place the laser waist on the photocathode, and taking baseline performance measurements of the tantalum photocathode. Future research will examine the performance of the electron gun as a function of the photoemission laser profile, the photocathode material, and the geometry and voltages of the accelerating and focusing components in the electron gun. This report presents the team's progress and outlines the work that remains.

  5. Exploring Electron Transfer in Organic Semiconductors | MIT-Harvard Center

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    for Excitonics Electron Transfer in Organic Semiconductors January 28, 2009 at 3pm/36-428 Troy Van Voorhis Department of Chemistry, Massachusetts Institute of Technology vanvoorhis2_000 abstract: Electron transfer reactions are the centerpiece of artificial photosynthetic complexes, organic LEDs and essentially all of redox chemistry. In particular, electron transfer rates govern the efficiency of exciton formation and dissociation in organic semiconductors. This talk will highlight ongoing

  6. Mimicking the electron transfer chain in photosystem II with...

    Office of Scientific and Technical Information (OSTI)

    of water oxidation Citation Details In-Document Search Title: Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water ...

  7. Electronic Funds Transfer Authorization Form 4/2014

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Information Company Name or DBA: Address: CityStateZip: Internal Use Only Electronic Funds Transfer Authorization Form I, an authorized signer on the below account, hereby...

  8. Electronic overfill protection for crude oil transfer

    SciTech Connect (OSTI)

    Kilgore, D.R.; Miles, D.C.

    1995-12-31

    There are many considerations involved in the transfer of crude oil, but the most catastrophic consequences may come as the result of a spill during loading or unloading. The safety and well-being of personnel in the vicinity is of the utmost concern. Should one be fortunate enough that an explosion or fire is not the results of a spill, the one must contend with the dilemma of containment. Preserving environmental integrity is a subject that is high on everyone`s list. The phrase ``reportable spill`` can send chills up and down anyone`s back. The repercussions continue: Ground water contamination; Soil remediation; Regulatory fines and penalties; Litigation. And this is all topped off by the ``black eye`` that the company receives with the perception of the public. For these reasons, and more, the carriers of crude oil are choosing self imposed compliances to reduce the frequency of spills. Electronic Overfill Protection has been modified to meet the specific needs and requirements of the crude oil industry. Here, the authors will examine how this type of system evolved, how it functions, and where it may lead.

  9. In-Situ Electrochemical Transmission Electron Microscopy for Battery Research

    SciTech Connect (OSTI)

    Mehdi, Beata L; Gu, Meng; Parent, Lucas; Xu, WU; Nasybulin, Eduard; Chen, Xilin; Unocic, Raymond R; Xu, Pinghong; Welch, David; Abellan, Patricia; Zhang, Ji-Guang; Liu, Jun; Wang, Chongmin; Arslan, Ilke; Evans, James E; Browning, Nigel

    2014-01-01

    The recent development of in-situ liquid stages for (scanning) transmission electron microscopes now makes it possible for us to study the details of electrochemical processes under operando conditions. As electrochemical processes are complex, care must be taken to calibrate the system before any in-situ/operando observations. In addition, as the electron beam can cause effects that look similar to electrochemical processes at the electrolyte/electrode interface, an understanding of the role of the electron beam in modifying the operando observations must also be understood. In this paper we describe the design, assembly, and operation of an in-situ electrochemical cell, paying particular attention to the method for controlling and quantifying the experimental parameters. The use of this system is then demonstrated for the lithiation/delithiation of silicon nanowires.

  10. Electron flow stability in magnetically insulated vacuum transmission lines

    SciTech Connect (OSTI)

    Rose, D. V.; Genoni, T. C.; Clark, R. E.; Welch, D. R. [Voss Scientific, LLC, Albuquerque, New Mexico 87108 (United States); Stygar, W. A. [Sandia National Laboratories, Albuquerque, New Mexico 87185 (United States)

    2011-03-15

    We evaluate the stability of electron current flow in high-power magnetically insulated transmission lines (MITLs). A detailed model of electron flow in cross-field gaps yields a dispersion relation for electromagnetic (EM) transverse magnetic waves [R. C. Davidson et al., Phys. Fluids 27, 2332 (1984)] which is solved numerically to obtain growth rates for unstable modes in various sheath profiles. These results are compared with two-dimensional (2D) EM particle-in-cell (PIC) simulations of electron flow in high-power MITLs. We find that the macroscopic properties (charge and current densities and self-fields) of the equilibrium profiles observed in the simulations are well represented by the laminar-flow model of Davidson et al. Idealized simulations of sheared flow in electron sheaths yield growth rates for both long (diocotron) and short (magnetron) wavelength instabilities that are in good agreement with the dispersion analysis. We conclude that electron sheaths that evolve self-consistently from space-charged-limited emission of electrons from the cathode in well-resolved 2D EM PIC simulations form stable profiles.

  11. Electron flow stability in magnetically insulated vacuum transmission lines.

    SciTech Connect (OSTI)

    Genoni, Thomas C. (Voss Scientific, LLC, Albuquerque, NM); Stygar, William A.; Welch, Dale Robert (Voss Scientific, LLC, Albuquerque, NM); Clark, R. E. (Voss Scientific, LLC, Albuquerque, NM); Rose, David V. (Voss Scientific, LLC, Albuquerque, NM)

    2010-11-01

    We evaluate the stability of electron current flow in high-power magnetically insulated transmission lines (MITLs). A detailed model of electron flow in cross-field gaps yields a dispersion relation for electromagnetic (EM) transverse magnetic waves [R. C. Davidson et al., Phys. Fluids 27, 2332 (1984)] which is solved numerically to obtain growth rates for unstable modes in various sheath profiles. These results are compared with two-dimensional (2D) EM particle-in-cell (PIC) simulations of electron flow in high-power MITLs. We find that the macroscopic properties (charge and current densities and self-fields) of the equilibrium profiles observed in the simulations are well represented by the laminar-flow model of Davidson et al. Idealized simulations of sheared flow in electron sheaths yield growth rates for both long (diocotron) and short (magnetron) wavelength instabilities that are in good agreement with the dispersion analysis. We conclude that electron sheaths that evolve self-consistently from space-charged-limited emission of electrons from the cathode in well-resolved 2D EM PIC simulations form stable profiles.

  12. Simultaneous orientation and thickness mapping in transmission electron microscopy

    SciTech Connect (OSTI)

    Tyutyunnikov, Dmitry; Özdöl, V. Burak; Koch, Christoph T.

    2014-12-04

    In this paper we introduce an approach for simultaneous thickness and orientation mapping of crystalline samples by means of transmission electron microscopy. We show that local thickness and orientation values can be extracted from experimental dark-field (DF) image data acquired at different specimen tilts. The method has been implemented to automatically acquire the necessary data and then map thickness and crystal orientation for a given region of interest. We have applied this technique to a specimen prepared from a commercial semiconductor device, containing multiple 22 nm technology transistor structures. The performance and limitations of our method are discussed and compared to those of other techniques available.

  13. Combined Scanning Transmission Electron Microscopy Tilt- and Focal Series

    SciTech Connect (OSTI)

    Dahmen, Tim; Baudoin, Jean-Pierre G; Lupini, Andrew R; Kubel, Christian; Slusallek, Phillip; De Jonge, Niels

    2014-01-01

    In this study, a combined tilt- and focal series is proposed as a new recording scheme for high-angle annular dark-field scanning transmission electron microscopy (STEM) tomography. Three-dimensional (3D) data were acquired by mechanically tilting the specimen, and recording a through-focal series at each tilt direction. The sample was a whole-mount macrophage cell with embedded gold nanoparticles. The tilt focal algebraic reconstruction technique (TF-ART) is introduced as a new algorithm to reconstruct tomograms from such combined tilt- and focal series. The feasibility of TF-ART was demonstrated by 3D reconstruction of the experimental 3D data. The results were compared with a conventional STEM tilt series of a similar sample. The combined tilt- and focal series led to smaller missing wedge artifacts, and a higher axial resolution than obtained for the STEM tilt series, thus improving on one of the main issues of tilt series-based electron tomography.

  14. Transmission electron microscope sample holder with optical features

    DOE Patents [OSTI]

    Milas, Mirko; Zhu, Yimei; Rameau, Jonathan David

    2012-03-27

    A sample holder for holding a sample to be observed for research purposes, particularly in a transmission electron microscope (TEM), generally includes an external alignment part for directing a light beam in a predetermined beam direction, a sample holder body in optical communication with the external alignment part and a sample support member disposed at a distal end of the sample holder body opposite the external alignment part for holding a sample to be analyzed. The sample holder body defines an internal conduit for the light beam and the sample support member includes a light beam positioner for directing the light beam between the sample holder body and the sample held by the sample support member.

  15. Simultaneous orientation and thickness mapping in transmission electron microscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Tyutyunnikov, Dmitry; Özdöl, V. Burak; Koch, Christoph T.

    2014-12-04

    In this paper we introduce an approach for simultaneous thickness and orientation mapping of crystalline samples by means of transmission electron microscopy. We show that local thickness and orientation values can be extracted from experimental dark-field (DF) image data acquired at different specimen tilts. The method has been implemented to automatically acquire the necessary data and then map thickness and crystal orientation for a given region of interest. We have applied this technique to a specimen prepared from a commercial semiconductor device, containing multiple 22 nm technology transistor structures. The performance and limitations of our method are discussed and comparedmore » to those of other techniques available.« less

  16. Mimicking the electron transfer chain in photosystem II with...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Megiatto, J. D., Antoniuk-Pablant, A., Sherman, B. D., Kodis, G., Gervaldo, M., Moore, T. A., Moore, A. L., and Gust, D. Title: Mimicking the electron transfer chain in...

  17. Rudolph A. Marcus and His Theory of Electron Transfer Reactions

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Rudolph A. Marcus and His Theory of Electron Transfer Reactions Resources with Additional Information * Interviews * Marcus Theory Rudolph A. Marcus Courtesy of Brookhaven National Laboratory Rudolph A. Marcus was awarded the 1992 Nobel Prize in Chemistry "for his contributions to the theory of electron transfer reactions in chemical systems". 'According to Chemistry Chairman Norman Sutin, some of the early definitive tests of Marcus's theoretical work were done ... at [Brookhaven

  18. Light-harvesting, Excitation Energy/Electron Transfer, and Photoregulation

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    in Artificial Photosynthetic Systems Light-harvesting, Excitation Energy/Electron Transfer, and Photoregulation in Artificial Photosynthetic Systems Authors: Terazono, Y., Moore, T. A., Moore, A.L., and Gust, D. Title: Light-harvesting, Excitation Energy/Electron Transfer, and Photoregulation in Artificial Photosynthetic Systems Source: Year: 2012 Volume: In: Multiporphyrin Arrays: Fundamentals and Applications edited by Dongho Kim, Pan Stanford Publishing Pages: 349-387 ABSTRACT: This

  19. High Cycle Fatigue in the Transmission Electron Microscope

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Bufford, Daniel C.; Stauffer, Douglas; Mook, William M.; Syed Asif, S. A.; Boyce, Brad L.; Hattar, Khalid

    2016-06-28

    One of the most common causes of structural failure in metals is fatigue induced by cyclic loading. Historically, microstructure-level analysis of fatigue cracks has primarily been performed post mortem. However, such investigations do not directly reveal the internal structural processes at work near micro- and nanoscale fatigue cracks and thus do not provide direct evidence of active microstructural mechanisms. In this paper, the tension–tension fatigue behavior of nanocrystalline Cu was monitored in real time at the nanoscale by utilizing a new capability for quantitative cyclic mechanical loading performed in situ in a transmission electron microscope (TEM). Controllable loads were appliedmore » at frequencies from one to several hundred hertz, enabling accumulations of 106 cycles within 1 h. The nanometer-scale spatial resolution of the TEM allows quantitative fatigue crack growth studies at very slow crack growth rates, measured here at ~10–12 m·cycle–1. This represents an incipient threshold regime that is well below the tensile yield stress and near the minimum conditions for fatigue crack growth. Evidence of localized deformation and grain growth within 150 nm of the crack tip was observed by both standard imaging and precession electron diffraction orientation mapping. Finally, these observations begin to reveal with unprecedented detail the local microstructural processes that govern damage accumulation, crack nucleation, and crack propagation during fatigue loading in nanocrystalline Cu.« less

  20. Thin dielectric film thickness determination by advanced transmission electron microscopy

    SciTech Connect (OSTI)

    Diebold, A.C.; Foran, B.; Kisielowski, C.; Muller, D.; Pennycook, S.; Principe, E.; Stemmer, S.

    2003-09-01

    High Resolution Transmission Electron Microscopy (HR-TEM) has been used as the ultimate method of thickness measurement for thin films. The appearance of phase contrast interference patterns in HR-TEM images has long been confused as the appearance of a crystal lattice by non-specialists. Relatively easy to interpret crystal lattice images are now directly observed with the introduction of annular dark field detectors for scanning TEM (STEM). With the recent development of reliable lattice image processing software that creates crystal structure images from phase contrast data, HR-TEM can also provide crystal lattice images. The resolution of both methods was steadily improved reaching now into the sub Angstrom region. Improvements in electron lens and image analysis software are increasing the spatial resolution of both methods. Optimum resolution for STEM requires that the probe beam be highly localized. In STEM, beam localization is enhanced by selection of the correct aperture. When STEM measurement is done using a highly localized probe beam, HR-TEM and STEM measurement of the thickness of silicon oxynitride films agree within experimental error. In this paper, the optimum conditions for HR-TEM and STEM measurement are discussed along with a method for repeatable film thickness determination. The impact of sample thickness is also discussed. The key result in this paper is the proposal of a reproducible method for film thickness determination.

  1. Transmission electron microscopy of whiskers and hillocks formed on Al films deposited onto a glass

    SciTech Connect (OSTI)

    Saka, H.; Fujino, S.; Kuroda, K. [Department of Quantum Engineering, Nagoya University, Nagoya 464-01 (Japan); Tsujimoto, K.; Tsuji, S. [Display Technology, IBM Japan, Ltd., Shimotsuruma, Yamato, Kanagawa 242 (Japan); Takatsuji, H. [Display Technology, IBM Japan, Ltd., Ichimiyake, Yasu-gun, Shiga 520-23 (Japan)

    1998-01-05

    Whiskers and hillocks formed on an Al film deposited onto a glass substrate have been observed by means of a variety of transmission electron microscopy technique.

  2. Transmission electron microscopy analysis of corroded metal waste forms.

    SciTech Connect (OSTI)

    Dietz, N. L.

    2005-04-15

    This report documents the results of analyses with transmission electron microscopy (TEM) combined with energy dispersive X-ray spectroscopy (EDS) and selected area electron diffraction (ED) of samples of metallic waste form (MWF) materials that had been subjected to various corrosion tests. The objective of the TEM analyses was to characterize the composition and microstructure of surface alteration products which, when combined with other test results, can be used to determine the matrix corrosion mechanism. The examination of test samples generated over several years has resulted in refinements to the TEM sample preparation methods developed to preserve the orientation of surface alteration layers and the underlying base metal. The preservation of microstructural spatial relationships provides valuable insight for determining the matrix corrosion mechanism and for developing models to calculate radionuclide release in repository performance models. The TEM results presented in this report show that oxide layers are formed over the exposed steel and intermetallic phases of the MWF during corrosion in aqueous solutions and humid air at elevated temperatures. An amorphous non-stoichiometric ZrO{sub 2} layer forms at the exposed surfaces of the intermetallic phases, and several nonstoichiometric Fe-O layers form over the steel phases in the MWF. These oxide layers adhere strongly to the underlying metal, and may be overlain by one or more crystalline Fe-O phases that probably precipitated from solution. The layer compositions are consistent with a corrosion mechanism of oxidative dissolution of the steel and intermetallic phases. The layers formed on the steel and intermetallic phases form a continuous layer over the exposed waste form, although vertical splits in the layer and corrosion in pits and crevices were seen in some samples. Additional tests and analyses are needed to verify that these layers passivate the underlying metals and if passivation can break

  3. TRANSMISSION ELECTRON MICROSCOPY STUDY OF HELIUM BEARING FUSION WELDS

    SciTech Connect (OSTI)

    Tosten, M; Michael Morgan, M

    2008-12-12

    A transmission electron microscopy (TEM) study was conducted to characterize the helium bubble distributions in tritium-charged-and-aged 304L and 21Cr-6Ni-9Mn stainless steel fusion welds containing approximately 150 appm helium-3. TEM foils were prepared from C-shaped fracture toughness test specimens containing {delta} ferrite levels ranging from 4 to 33 volume percent. The weld microstructures in the low ferrite welds consisted mostly of austenite and discontinuous, skeletal {delta} ferrite. In welds with higher levels of {delta} ferrite, the ferrite was more continuous and, in some areas of the 33 volume percent sample, was the matrix/majority phase. The helium bubble microstructures observed were similar in all samples. Bubbles were found in the austenite but not in the {delta} ferrite. In the austenite, bubbles had nucleated homogeneously in the grain interiors and heterogeneously on dislocations. Bubbles were not found on any austenite/austenite grain boundaries or at the austenite/{delta} ferrite interphase interfaces. Bubbles were not observed in the {delta} ferrite because of the combined effects of the low solubility and rapid diffusion of tritium through the {delta} ferrite which limited the amount of helium present to form visible bubbles.

  4. A TRANSMISSION ELECTRON MICROSCOPY STUDY OF PRESOLAR HIBONITE

    SciTech Connect (OSTI)

    Zega, Thomas J.; Stroud, Rhonda M.; Alexander, Conel M. O'D.; Nittler, Larry R.

    2011-04-01

    We report isotopic and microstructural data on five presolar hibonite grains (KH1, KH2, KH6, KH15, and KH21) identified in an acid residue of the Krymka LL3.1 ordinary chondrite. Isotopic measurements by secondary ion mass spectrometry (SIMS) verified a presolar circumstellar origin for the grains. Transmission electron microscopy (TEM) examination of the crystal structure and chemistry of the grains was enabled by in situ sectioning and lift-out with a focused-ion-beam scanning-electron microscope (FIB-SEM). Comparisons of isotopic compositions with models indicate that four of the five grains formed in low-mass stars that evolved through the red giant/asymptotic giant branches (RGBs/AGBs), whereas one grain formed in the ejecta of a Type II supernova. Selected-area electron-diffraction patterns show that all grains are single crystals of hibonite. Some grains contain minor structural perturbations (stacking faults) and small spreads in orientation that can be attributed to a combination of growth defects and mechanical processing by grain-grain collisions. The similar structure of the supernova grain to those from RGB/AGB stars indicates a similarity in the formation conditions. Radiation damage (e.g., point defects), if present, occurs below our detection limit. Of the five grains we studied, only one has the pure hibonite composition of CaAl{sub 12}O{sub 19}. All others contain minor amounts of Mg, Si, Ti, and Fe. The microstructural data are generally consistent with theoretical predictions, which constrain the circumstellar condensation temperature to a range of 1480-1743 K, assuming a corresponding total gas pressure between 1 x 10{sup -6} and 1 x 10{sup -3} atm. The TEM data were also used to develop a calibration for SIMS determination of Ti contents in oxide grains. Grains with extreme {sup 18}O depletions, indicating deep mixing has occurred in their parent AGB stars, are slightly Ti enriched compared with grains from stars without deep mixing, most

  5. Electron transfer statistics and thermal fluctuations in molecular junctions

    SciTech Connect (OSTI)

    Goswami, Himangshu Prabal; Harbola, Upendra

    2015-02-28

    We derive analytical expressions for probability distribution function (PDF) for electron transport in a simple model of quantum junction in presence of thermal fluctuations. Our approach is based on the large deviation theory combined with the generating function method. For large number of electrons transferred, the PDF is found to decay exponentially in the tails with different rates due to applied bias. This asymmetry in the PDF is related to the fluctuation theorem. Statistics of fluctuations are analyzed in terms of the Fano factor. Thermal fluctuations play a quantitative role in determining the statistics of electron transfer; they tend to suppress the average current while enhancing the fluctuations in particle transfer. This gives rise to both bunching and antibunching phenomena as determined by the Fano factor. The thermal fluctuations and shot noise compete with each other and determine the net (effective) statistics of particle transfer. Exact analytical expression is obtained for delay time distribution. The optimal values of the delay time between successive electron transfers can be lowered below the corresponding shot noise values by tuning the thermal effects.

  6. Theory of ultrafast heterogeneous electron transfer: Contributions of direct charge transfer excitations to the absorbance

    SciTech Connect (OSTI)

    Wang, Luxia; Willig, Frank; May, Volkhard

    2007-04-07

    Absorption spectra related to heterogeneous electron transfer are analyzed with the focus on direct charge transfer transition from the surface attached molecule into the semiconductor band states. The computations are based on a model of reduced dimensionality with a single intramolecular vibrational coordinate but a complete account for the continuum of conduction band states. The applicability of this model to perylene on TiO{sub 2} has been demonstrated in a series of earlier papers. Here, based on a time-dependent formulation, the absorbance is calculated with the inclusion of charge transfer excitations. A broad parameter set inspired by the perylene TiO{sub 2} systems is considered. In particular, the description generalizes the Fano effect to heterogeneous electron transfer reactions. Preliminary simulations of measured spectra are presented for perylene-catechol attached to TiO{sub 2}.

  7. CORRELATING ELECTRONIC AND VIBRATIONAL MOTIONS IN CHARGE TRANSFER SYSTEMS

    SciTech Connect (OSTI)

    Khalil, Munira

    2014-06-27

    The goal of this research program was to measure coupled electronic and nuclear motions during photoinduced charge transfer processes in transition metal complexes by developing and using novel femtosecond spectroscopies. The scientific highlights and the resulting scientific publications from the DOE supported work are outlined in the technical report.

  8. Soliton propagation, reflection, and transmission in an inhomogeneous plasma with trapped electrons

    SciTech Connect (OSTI)

    Aziz, Farah; Malik, Hitendra K.; Stroth, Ulrich

    2011-04-15

    Transmission and reflection of solitons from a semitransparent grid in an inhomogeneous plasma in the presence of trapped electrons is studied analytically. Conditions are obtained for the obliqueness of the propagation and the drift velocity of ions for the soliton transmission and reflection. Also, a transmission-reflection conservation law is derived. The contribution of trapped electrons to the solitons' propagation and their reflection and transmission is examined through energy, amplitude, and width of the solitons, in addition to the effect of temperature and drift of the ions.

  9. A single-shot transmissive spectrometer for hard x-ray free electron...

    Office of Scientific and Technical Information (OSTI)

    Results Journal Article: A single-shot transmissive spectrometer for hard x-ray free electron lasers Citation Details ... We report hard x-ray single-shot spectral measurements of ...

  10. Hot Electron Transfer from Semiconductor Nanocrystals | MIT-Harvard Center

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    for Excitonics Hot Electron Transfer from Semiconductor Nanocrystals March 30, 2010 at 3pm/36-428 William A. Tisdale Department of Chemical Engineering and Materials Science University of Minnesota tisdale_002 abstract: In conventional semiconductor solar cells, absorption of photons with energies greater than the semiconductor band gap generate "hot" charge carriers that quickly "cool" before all of their energy can be captured - a process that limits device efficiency.

  11. Comparing the Primary Electron Transfer Process in Organic Photovoltaic

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Heterojunctions with Photosynthetic Reaction Centers | MIT-Harvard Center for Excitonics Comparing the Primary Electron Transfer Process in Organic Photovoltaic Heterojunctions with Photosynthetic Reaction Centers October 4, 2011 at 3pm/36-428 Garry Rumbles National Renewable Energy Laboratory (NREL), Univeristy of Colorado, Boulder rumbles002 Abstract: This presentation will focus on some of the fundamental science associated with the rapidly emerging field of organic photovoltaics (OPV).

  12. Big Data Analytics for Scanning Transmission Electron Microscopy Ptychography

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Jesse, S.; Chi, M.; Belianinov, A.; Beekman, C.; Kalinin, S. V.; Borisevich, A. Y.; Lupini, A. R.

    2016-05-23

    Electron microscopy is undergoing a transition; from the model of producing only a few micrographs, through the current state where many images and spectra can be digitally recorded, to a new mode where very large volumes of data (movies, ptychographic and multi-dimensional series) can be rapidly obtained. In this paper, we discuss the application of so-called “big-data” methods to high dimensional microscopy data, using unsupervised multivariate statistical techniques, in order to explore salient image features in a specific example of BiFeO3 domains. Remarkably, k-means clustering reveals domain differentiation despite the fact that the algorithm is purely statistical in nature andmore » does not require any prior information regarding the material, any coexisting phases, or any differentiating structures. While this is a somewhat trivial case, this example signifies the extraction of useful physical and structural information without any prior bias regarding the sample or the instrumental modality. Further interpretation of these types of results may still require human intervention. Finally, however, the open nature of this algorithm and its wide availability, enable broad collaborations and exploratory work necessary to enable efficient data analysis in electron microscopy.« less

  13. Aberration corrected 1.2-MV cold field-emission transmission electron microscope with a sub-50-pm resolution

    SciTech Connect (OSTI)

    Akashi, Tetsuya; Takahashi, Yoshio; Tanigaki, Toshiaki Shimakura, Tomokazu; Kawasaki, Takeshi; Furutsu, Tadao; Shinada, Hiroyuki; Osakabe, Nobuyuki; Mller, Heiko; Haider, Maximilian; Tonomura, Akira

    2015-02-16

    Atomic-resolution electromagnetic field observation is critical to the development of advanced materials and to the unveiling of their fundamental physics. For this purpose, a spherical-aberration corrected 1.2-MV cold field-emission transmission electron microscope has been developed. The microscope has the following superior properties: stabilized accelerating voltage, minimized electrical and mechanical fluctuation, and coherent electron emission. These properties have enabled to obtain 43-pm information transfer. On the bases of these performances, a 43-pm resolution has been obtained by correcting lens aberrations up to the third order. Observations of GaN [411] thin crystal showed a projected atomic locations with a separation of 44?pm.

  14. Imaging and microanalysis of thin ionomer layers by scanning transmission electron microscopy

    SciTech Connect (OSTI)

    Cullen, David A; Koestner, Roland; Kukreja, Ratan; Minko, Sergiy; Trotsenko, Oleksandr; Tokarev, Alexander V; Guetaz, Laure; Meyer III, Harry M; Parish, Chad M; More, Karren Leslie

    2014-01-01

    Improved conditions for imaging and spectroscopic mapping of thin perfluorosulfonic acid (PFSA) ionomer layers in fuel cell electrodes by scanning transmission electron microscopy (STEM) have been investigated. These conditions are first identified on model systems of Nafion ionomer-coated nanostructured thin films and nanoporous Si. The optimized conditions are then applied in a quantitative study of the ionomer through-layer loading for two typical electrode catalyst coatings using electron energy loss and energy dispersive X-ray spectroscopy in the transmission electron microscope. The e-beam induced damage to the perfluorosulfonic acid (PFSA) ionomer is quantified by following the fluorine mass loss with electron exposure and is then mitigated by a few orders of magnitude using cryogenic specimen cooling and a higher incident electron voltage. Multivariate statistical analysis is also applied to the analysis of spectrum images for data denoising and unbiased separation of independent components related to the catalyst, ionomer, and support.

  15. Characterization of aluminum oxide tunnel barriers by combining transport measurements and transmission electron microscopy imaging

    SciTech Connect (OSTI)

    Aref, T.; Averin, A.; Nguyend, H. Q.; Pekola, J. P.; Dijken, S. van; Yao, L. D.; Ferring, A.; Koberidze, M.; Nieminen, R. M.

    2014-08-21

    We present two approaches for studying the uniformity of a tunnel barrier. The first approach is based on measuring single-electron and two-electron tunneling in a hybrid single-electron transistor. Our measurements indicate that the effective area of a conduction channel is about one order of magnitude larger than predicted by theoretical calculations. With the second method, transmission electron microscopy, we demonstrate that variations in the barrier thickness are a plausible explanation for the larger effective area and an enhancement of higher order tunneling processes.

  16. Transferred metal electrode films for large-area electronic devices...

    Office of Scientific and Technical Information (OSTI)

    We show here that the self-release layer transfer method recently developed for high-quality graphene transfer is also capable of giving high-quality metal thin-film transfers to ...

  17. A stochastic reorganizational bath model for electronic energy transfer

    SciTech Connect (OSTI)

    Fujita, Takatoshi E-mail: aspuru@chemistry.harvard.edu; Huh, Joonsuk; Aspuru-Guzik, Aln E-mail: aspuru@chemistry.harvard.edu

    2014-06-28

    Environmentally induced fluctuations of the optical gap play a crucial role in electronic energy transfer dynamics. One of the simplest approaches to incorporate such fluctuations in energy transfer dynamics is the well known Haken-Strobl-Reineker (HSR) model, in which the energy-gap fluctuation is approximated as white noise. Recently, several groups have employed molecular dynamics simulations and excited-state calculations in conjunction to account for excitation energies thermal fluctuations. On the other hand, since the original work of HSR, many groups have employed stochastic models to simulate the same transfer dynamics. Here, we discuss a rigorous connection between the stochastic and the atomistic bath models. If the phonon bath is treated classically, time evolution of the exciton-phonon system can be described by Ehrenfest dynamics. To establish the relationship between the stochastic and atomistic bath models, we employ a projection operator technique to derive the generalized Langevin equations for the energy-gap fluctuations. The stochastic bath model can be obtained as an approximation of the atomistic Ehrenfest equations via the generalized Langevin approach. Based on this connection, we propose a novel scheme to take account of reorganization effects within the framework of stochastic models. The proposed scheme provides a better description of the population dynamics especially in the regime of strong exciton-phonon coupling. Finally, we discuss the effect of the bath reorganization in the absorption and fluorescence spectra of ideal J-aggregates in terms of the Stokes shifts. We find a simple expression that relates the reorganization contribution to the Stokes shifts the reorganization shift to the ideal or non-ideal exciton delocalization in a J-aggregate. The reorganization shift can be described by three parameters: the monomer reorganization energy, the relaxation time of the optical gap, and the exciton delocalization length. This

  18. Light-induced electron transfer vs. energy transfer in molecular thin-film systems

    SciTech Connect (OSTI)

    Renschler, C. L.; Faulkner, L. R.

    1980-01-01

    Quenching of fluoranthene (FA) singlets by tetrabromo-o-benzoquinone (TBBQ) and N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) was studied both in xylene solutions and in spin-cast polystyrene (PS) films. Emphasis was placed on time-resolved fluorescence transients resulting from pulsed excitation. Linear Stern-Volmer plots were obtained for quenching in solution and gave diffusion-controlled rate constants, of 1.45 x 10/sup 10/ M/sup -1/ sec/sup -1/ and 1.53 x 10/sup 10/ M/sup -1/ sec/sup -1/ for TBBQ and TMPD, respectively. TBBQ was found to quench FA singlets in PS over the studied concentration range 12 mM < (TBBQ) < 48 mM, but in its presence FA singlets decayed nonexponentially. The results were interpreted quantitatively in terms of pure Foerster's transfer from FA to TBBQ without diffusion of excitons. The critical transfer radius R/sub 0/ was experimentally determined to be 24.3 A, which is in good agreement with the theoretical value of 23 A calculated from spectral data. Quenching of FA singlets in PS films was found to be independent of FA concentration over a 300 mM to 1200 mM FA concentration range for a constant TBBQ concentration of 24.0 mM. TMPD was only slightly effective as a quencher of FA singlets in PS because it apparently behaves strictly as a contact quencher based on reversible charge transfer. The implications of these results for the design of systems intended to exploit light-induced electron transfer are discussed.

  19. Method and apparatus for a high-resolution three dimensional confocal scanning transmission electron microscope

    SciTech Connect (OSTI)

    de Jonge, Niels

    2010-08-17

    A confocal scanning transmission electron microscope which includes an electron illumination device providing an incident electron beam propagating in a direction defining a propagation axis, and a precision specimen scanning stage positioned along the propagation axis and movable in at least one direction transverse to the propagation axis. The precision specimen scanning stage is configured for positioning a specimen relative to the incident electron beam. A projector lens receives a transmitted electron beam transmitted through at least part of the specimen and focuses this transmitted beam onto an image plane, where the transmitted beam results from the specimen being illuminated by the incident electron beam. A detection system is placed approximately in the image plane.

  20. Investigating the mesostructure of ordered porous silica nanocomposites by transmission electron microscopy techniques

    SciTech Connect (OSTI)

    Bullita, S.; Casula, M. F.; Piludu, M.; Falqui, A.; Carta, D.; Corrias, A.

    2014-10-21

    Nanocomposites made out of FeCo alloy nanocrystals supported onto pre-formed mesoporous ordered silica which features a cubic arrangement of pores (SBA-16) were investigated. Information on the effect of the nanocrystals on the mesostructure (i.e. pore arrangement symmetry, pore size, and shape) were deduced by a multitechnique approach including N2 physisorption, low angle X-ray diffraction, and Transmission electron microscopy. It is shown that advanced transmission electron microscopy techniques are required, however, to gain direct evidence on key compositional and textural features of the nanocomposites. In particular, electron tomography and microtomy techniques make clear that the FeCo nanocrystals are located within the pores of the SBA-16 silica, and that the ordered mesostructure of the nanocomposite is retained throughout the observed specimen.

  1. Thermal transfer structures coupling electronics card(s) to coolant-cooled structure(s)

    DOE Patents [OSTI]

    David, Milnes P; Graybill, David P; Iyengar, Madhusudan K; Kamath, Vinod; Kochuparambil, Bejoy J; Parida, Pritish R; Schmidt, Roger R

    2014-12-16

    Cooling apparatuses and coolant-cooled electronic systems are provided which include thermal transfer structures configured to engage with a spring force one or more electronics cards with docking of the electronics card(s) within a respective socket(s) of the electronic system. A thermal transfer structure of the cooling apparatus includes a thermal spreader having a first thermal conduction surface, and a thermally conductive spring assembly coupled to the conduction surface of the thermal spreader and positioned and configured to reside between and physically couple a first surface of an electronics card to the first surface of the thermal spreader with docking of the electronics card within a socket of the electronic system. The thermal transfer structure is, in one embodiment, metallurgically bonded to a coolant-cooled structure and facilitates transfer of heat from the electronics card to coolant flowing through the coolant-cooled structure.

  2. Nanoscale deformation analysis with high-resolution transmission electron microscopy and digital image correlation

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Wang, Xueju; Pan, Zhipeng; Fan, Feifei; Wang, Jiangwei; Liu, Yang; Mao, Scott X.; Zhu, Ting; Xia, Shuman

    2015-09-10

    We present an application of the digital image correlation (DIC) method to high-resolution transmission electron microscopy (HRTEM) images for nanoscale deformation analysis. The combination of DIC and HRTEM offers both the ultrahigh spatial resolution and high displacement detection sensitivity that are not possible with other microscope-based DIC techniques. We demonstrate the accuracy and utility of the HRTEM-DIC technique through displacement and strain analysis on amorphous silicon. Two types of error sources resulting from the transmission electron microscopy (TEM) image noise and electromagnetic-lens distortions are quantitatively investigated via rigid-body translation experiments. The local and global DIC approaches are applied for themore » analysis of diffusion- and reaction-induced deformation fields in electrochemically lithiated amorphous silicon. As a result, the DIC technique coupled with HRTEM provides a new avenue for the deformation analysis of materials at the nanometer length scales.« less

  3. Nanoscale deformation analysis with high-resolution transmission electron microscopy and digital image correlation

    SciTech Connect (OSTI)

    Wang, Xueju; Pan, Zhipeng; Fan, Feifei; Wang, Jiangwei; Liu, Yang; Mao, Scott X.; Zhu, Ting; Xia, Shuman

    2015-09-10

    We present an application of the digital image correlation (DIC) method to high-resolution transmission electron microscopy (HRTEM) images for nanoscale deformation analysis. The combination of DIC and HRTEM offers both the ultrahigh spatial resolution and high displacement detection sensitivity that are not possible with other microscope-based DIC techniques. We demonstrate the accuracy and utility of the HRTEM-DIC technique through displacement and strain analysis on amorphous silicon. Two types of error sources resulting from the transmission electron microscopy (TEM) image noise and electromagnetic-lens distortions are quantitatively investigated via rigid-body translation experiments. The local and global DIC approaches are applied for the analysis of diffusion- and reaction-induced deformation fields in electrochemically lithiated amorphous silicon. As a result, the DIC technique coupled with HRTEM provides a new avenue for the deformation analysis of materials at the nanometer length scales.

  4. In situ transmission electron microscopy of individual carbon nanotetrahedron/nanoribbon structures in Joule heating

    SciTech Connect (OSTI)

    Masuda, Yusuke; Yoshida, Hideto; Takeda, Seiji; Kohno, Hideo

    2014-08-25

    Collapse of a carbon nanotube results in the formation of a nanoribbon, and a switching of the collapse direction yields a nanotetrahedron in the middle of a nanoribbon. Here, we report in-situ transmission electron microscopy observations of the behavior of carbon nanotetrahedron/nanoribbon structures during Joule heating to reveal their thermal stability. In addition, we propose that the observed process is related to the formation process of the structure.

  5. Comparison of preparation techniques for nuclear materials for transmission electron microscopy (TEM)

    SciTech Connect (OSTI)

    Aitkaliyeva, Assel; Madden, James W.; Miller, Brandon D; Cole, James I; Gan, Jian

    2015-04-01

    Preparation of highly radioactive and irradiated nuclear fuels and materials for transmission electron microscopy (TEM) is conjoined with a set of unique challenges, including but not limited to personnel radiation exposure and contamination. The paper evaluates three specimen preparation techniques for preparation of irradiated materials and determines which technique yields to the most reliable characterization of radiation damage microstructure. Various specimen preparation artifacts associated with each technique are considered and ways of minimizing these artifacts are addressed.

  6. Defects in paramagnetic Co-doped ZnO films studied by transmission electron microscopy

    SciTech Connect (OSTI)

    Kovacs, Andras; Ney, A.; Duchamp, Martial; Ney, V.; Boothroyd, Chris; Galindo, Pedro L.; Kaspar, Tiffany C.; Chambers, Scott A.; Dunin-Borkowski, Rafal

    2013-12-23

    We have studied planar defects in epitaxial Co:ZnO dilute magnetic semiconductor thin films deposited on c-plane sapphire (Al2O3) and the Co:ZnO/Al2O3 interface structure at atomic resolution using aberration-corrected transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS). Comparing Co:ZnO samples deposited by pulsed laser deposition and reactive magnetron sputtering, both exhibit extrinsic stacking faults, incoherent interface structures, and compositional variations within the first 3-4 Co:ZnO layers at the interface.. In addition, we have measured the local strain which reveals the lattice distortion around the stacking faults.

  7. Concurrent in situ ion irradiation transmission electron microscope

    SciTech Connect (OSTI)

    Hattar, K.; Bufford, D. C.; Buller, D. L.

    2014-08-29

    An in situ ion irradiation transmission electron microscope has been developed and is operational at Sandia National Laboratories. This facility permits high spatial resolution, real time observation of electron transparent samples under ion irradiation, implantation, mechanical loading, corrosive environments, and combinations thereof. This includes the simultaneous implantation of low-energy gas ions (0.830 keV) during high-energy heavy ion irradiation (0.848 MeV). In addition, initial results in polycrystalline gold foils are provided to demonstrate the range of capabilities.

  8. Efficient linear phase contrast in scanning transmission electron microscopy with matched illumination and detector interferometry

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Ophus, Colin; Ciston, Jim; Pierce, Jordan; Harvey, Tyler R.; Chess, Jordan; McMorran, Benjamin J.; Czarnik, Cory; Rose, Harald H.; Ercius, Peter

    2016-02-29

    The ability to image light elements in soft matter at atomic resolution enables unprecedented insight into the structure and properties of molecular heterostructures and beam-sensitive nanomaterials. In this study, we introduce a scanning transmission electron microscopy technique combining a pre-specimen phase plate designed to produce a probe with structured phase with a high-speed direct electron detector to generate nearly linear contrast images with high efficiency. We demonstrate this method by using both experiment and simulation to simultaneously image the atomic-scale structure of weakly scattering amorphous carbon and strongly scattering gold nanoparticles. Our method demonstrates strong contrast for both materials, makingmore » it a promising candidate for structural determination of heterogeneous soft/hard matter samples even at low electron doses comparable to traditional phase-contrast transmission electron microscopy. Ultimately, simulated images demonstrate the extension of this technique to the challenging problem of structural determination of biological material at the surface of inorganic crystals.« less

  9. Nucleation of diamond by pure carbon ion bombardment--a transmission electron microscopy study

    SciTech Connect (OSTI)

    Yao, Y.; Liao, M.Y.; Wang, Z.G.; Lifshitz, Y.; Lee, S.

    2005-08-08

    A cross-sectional high-resolution transmission electron microscopy (HRTEM) study of a film deposited by a 1 keV mass-selected carbon ion beam onto silicon held at 800 deg. C is presented. Initially, a graphitic film with its basal planes perpendicular to the substrate is evolving. The precipitation of nanodiamond crystallites in upper layers is confirmed by HRTEM, selected area electron diffraction, and electron energy loss spectroscopy. The nucleation of diamond on graphitic edges as predicted by Lambrecht et al. [W. R. L. Lambrecht, C. H. Lee, B. Segall, J. C. Angus, Z. Li, and M. Sunkara, Nature, 364 607 (1993)] is experimentally confirmed. The results are discussed in terms of our recent subplantation-based diamond nucleation model.

  10. Structural defects in GaN revealed by Transmission Electron Microscopy

    SciTech Connect (OSTI)

    Liliental-Weber, Zuzanna

    2014-04-18

    This paper reviews the various types of structural defects observed by Transmission Electron Microscopy in GaN heteroepitaxial layers grown on foreign substrates and homoepitaxial layers grown on bulk GaN substrates. The structural perfection of these layers is compared to the platelet self-standing crystals grown by High Nitrogen Pressure Solution. Defects in undoped and Mg doped GaN are discussed. Some models explaining the formation of inversion domains in heavily Mg doped layers that are possible defects responsible for the difficulties of p-doping in GaN are also reviewed.

  11. Structural defects in GaN revealed by Transmission Electron Microscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Liliental-Weber, Zuzanna

    2014-09-08

    This paper reviews the various types of structural defects observed by Transmission Electron Microscopy in GaN heteroepitaxial layers grown on foreign substrates and homoepitaxial layers grown on bulk GaN substrates. The structural perfection of these layers is compared to the platelet self-standing crystals grown by High Nitrogen Pressure Solution. Defects in undoped and Mg doped GaN are discussed. Lastly, some models explaining the formation of inversion domains in heavily Mg doped layers that are possible defects responsible for the difficulties of p-doping in GaN are also reviewed.

  12. Studying The Kinetics Of Crystalline Silicon Nanoparticle Lithiation With In-Situ Transmission Electron Microscopy

    SciTech Connect (OSTI)

    Mcdowell, Matthew T.; Ryu, Ill; Lee, Seokwoo; Wang, Chong M.; Nix, William D.; Cui, Yi

    2012-11-27

    Silicon is an attractive high-capacity anode material for Li-ion batteries, but a comprehensive understanding of the massive ~300% volume change and fracture during lithiation/delithiation is necessary to reliably employ Si anodes. Here, in-situ transmission electron microscopy (TEM) of the lithiation of crystalline Si nanoparticles reveals that the reaction slows down as it progresses into the particle interior. Analysis suggests that this behavior is due to the influence of mechanical stress at the reaction front on the driving force for the reaction. These experiments give insight into the factors controlling the kinetics of this unique reaction.

  13. Gas mixing system for imaging of nanomaterials under dynamic environments by environmental transmission electron microscopy

    SciTech Connect (OSTI)

    Akatay, M. Cem; Zvinevich, Yury; Ribeiro, Fabio H. E-mail: estach@bnl.gov; Baumann, Philipp; Stach, Eric A. E-mail: estach@bnl.gov

    2014-03-15

    A gas mixing manifold system that is capable of delivering a stable pressure stream of a desired composition of gases into an environmental transmission electron microscope has been developed. The system is designed to provide a stable imaging environment upon changes of either the composition of the gas mixture or upon switching from one gas to another. The design of the system is described and the response of the pressure inside the microscope, the sample temperature, and sample drift in response to flow and composition changes of the system are reported.

  14. In situ transmission electron microscopy analysis of conductive filament during solid electrolyte resistance switching

    SciTech Connect (OSTI)

    Fujii, Takashi; Arita, Masashi; Takahashi, Yasuo; Fujiwara, Ichiro

    2011-05-23

    An in situ transmission electron microscopy (TEM) analysis of a solid electrolyte, Cu-GeS, during resistance switching is reported. Real-time observations of the filament formation and disappearance process were performed in the TEM instrument and the conductive-filament-formation model was confirmed experimentally. Narrow conductive filaments were formed corresponding to resistance switching from high- to low-resistance states. When the resistance changed to high-resistance state, the filament disappeared. It was also confirmed by use of selected area diffractometry and energy-dispersive x-ray spectroscopy that the conductive filament was made of nanocrystals composed mainly of Cu.

  15. Visualizing non-equilibrium lithiation of spinel oxide via in situ transmission electron microscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    He, Kai; Zhang, Sen; Li, Jing; Yu, Xiqian; Meng, Qingping; Zhu, Yizhou; Hu, Enyuan; Sun, Ke; Yun, Hongseok; Yang, Xiao -Qing; et al

    2016-05-09

    In this study, spinel transition metal oxides are an important class of materials that are being considered as electrodes for lithium-ion batteries, due to their low cost and high theoretical capacity. The lithiation of these compounds is known to undergo a two-step reaction, whereby intercalation and conversion occur in a sequential fashion. These two reactions are known to have distinct reaction dynamics, but it is unclear how the kinetics of these processes affect the overall electrochemical response. Here, we explore the lithiation of nanosized magnetite (Fe3O4) by employing a new strain-sensitive, bright-field scanning transmission electron microscopy approach.

  16. Center for Biological Electron Transfer and Catalysis (BETCy) | U.S. DOE

    Office of Science (SC) Website

    Office of Science (SC) Center for Biological Electron Transfer and Catalysis (BETCy) Energy Frontier Research Centers (EFRCs) EFRCs Home Centers EFRC External Websites Research Science Highlights News & Events Publications History Contact BES Home Centers Center for Biological Electron Transfer and Catalysis (BETCy) Print Text Size: A A A FeedbackShare Page BETCy Header Director John Peters Lead Institution Montana State University Year Established 2014 Mission To investigate the

  17. Electron Transfer Dynamics in Photocatalytic CO2 Conversion | netl.doe.gov

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Electron Transfer Dynamics in Photocatalytic CO2 Conversion Electron Transfer Dynamics in Photocatalytic CO2 Conversion Coal is the workhorse of our power industry, responsible for approximately half of the electricity consumed by Americans. Managing carbon dioxide (CO2) emissions from coal utilization is one of the most challenging issues facing the fossil energy industry today. To cost-effectively capture and manage CO2, new and flexible photocatalytic technologies are being developed that can

  18. Biological Applications and Transmission Electron Microscopy Investigations of Mesoporous Silica Nanoparticles

    SciTech Connect (OSTI)

    Brian G. Trewyn

    2006-05-01

    The research presented and discussed within involves the development of novel biological applications of mesoporous silica nanoparticles (MSN) and an investigation of mesoporous material by transmission electron microscopy (TEM). Mesoporous silica nanoparticles organically functionalized shown to undergo endocytosis in cancer cells and drug release from the pores was controlled intracellularly and intercellularly. Transmission electron microscopy investigations demonstrated the variety of morphologies produced in this field of mesoporous silica nanomaterial synthesis. A series of room-temperature ionic liquid (RTIL) containing mesoporous silica nanoparticle (MSN) materials with various particle morphologies, including spheres, ellipsoids, rods, and tubes, were synthesized. By changing the RTIL template, the pore morphology was tuned from the MCM-41 type of hexagonal mesopores to rotational moire type of helical channels, and to wormhole-like porous structures. These materials were used as controlled release delivery nanodevices to deliver antibacterial ionic liquids against Escherichia coli K12. The involvement of a specific organosiloxane function group, covalently attached to the exterior of fluorescein doped mesoporous silica nanoparticles (FITC-MSN), on the degree and kinetics of endocytosis in cancer and plant cells was investigated. The kinetics of endocystosis of TEG coated FITC-MSN is significantly quicker than FITC-MSN as determined by flow cytometry experiments. The fluorescence confocal microscopy investigation showed the endocytosis of TEG coated-FITC MSN triethylene glycol grafted fluorescein doped MSN (TEG coated-FITC MSN) into both KeLa cells and Tobacco root protoplasts. Once the synthesis of a controlled-release delivery system based on MCM-41-type mesoporous silica nanorods capped by disulfide bonds with superparamagnetic iron oxide nanoparticles was completed. The material was characterized by general methods and the dosage and kinetics of the

  19. Insights into proton-coupled electron transfer mechanisms of electrocatalytic H2 oxidation and production

    SciTech Connect (OSTI)

    Horvath, Samantha; Fernandez, Laura; Soudackov, Alexander V.; Hammes-Schiffer, Sharon

    2012-09-25

    The design of molecular electrocatalysts for H2 oxidation and production is important for the development of alternative renewable energy sources that are abundant, inexpensive, and environmentally benign. Recently nickel-based molecular electrocatalysts with pendant amines that act as proton relays for the nickel center were shown to effectively catalyze H2 oxidation and production. We developed a quantum mechanical approach for studying proton-coupled electron transfer processes in these types of molecular electrocatalysts. This theoretical approach is applied to a nickel-based catalyst in which phosphorous atoms are directly bonded to the nickel center and nitrogen atoms of the ligand rings act as proton relays. The cataly c step of interest involves electron transfer between the nickel complex and the electrode as well as intramolecular proton transfer between the nickel and nitrogen atoms. This process can occur sequentially, with either the electron or proton transferring first, or concertedly, with the electron and proton transferring simultaneously without a stable intermediate. The heterogeneous rate constants are calculated as functions of overpotential for the concerted electron-proton transfer reaction and the two electron transfer reactions in the sequential mechanisms. Our calculations illustrate that the concerted electron-proton transfer standard rate constant will increase as the equilibrium distance between the nickel and nitrogen atoms decreases and as the nitrogen atoms become more mobile to facilitate the contraction of this distance. This approach assists in the identification of the favored mechanisms under various experimental conditions and provides insight into the qualitative impact of substituents on the nitrogen and phosphorous atoms. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy

  20. Measured Radiation and Background Levels During Transmission of Megawatt Electron Beams Through Millimeter Apertures

    SciTech Connect (OSTI)

    Alarcon, Ricardo [Arizona State University, Glendale, AZ (United States); Balascuta, S. [Arizona State University, Glendale, AZ (United States); Benson, Stephen V. [Thomas Jefferson National Accelerator Facility, Newport News, VA (United States); Bertozzi, William [Massachusetts Institute of Technology, Cambridge, MA (United States); Boyce, James R. [Thomas Jefferson National Accelerator Facility, Newport News, VA (United States); Cowan, Ray [Massachusetts Institute of Technology, Cambridge, MA (United States); Douglas, David R. [Thomas Jefferson National Accelerator Facility, Newport News, VA (United States); Evtushenko, Pavel [Thomas Jefferson National Accelerator Facility, Newport News, VA (United States); Fisher, P. [Massachusetts Institute of Technology, Cambridge, MA (United States); Ihloff, Ernest E. [Hampton University, Hampton, VA (United States); Kalantarians, Narbe [Hampton University, Hampton, VA (United States); Kelleher, Aidan Michael [Massachusetts Institute of Technology, Cambridge, MA (United States); Krossler, W. J. [William and Mary College, Williamsburg, VA (United States); Legg, Robert A. [Thomas Jefferson National Accelerator Facility, Newport News, VA (United States); Long, Elena [University of New Hampshire, Durham, NH (United States); Milner, Richard [Massachusetts Institute of Technology, Cambridge, MA (United States); Neil, George R. [Thomas Jefferson National Accelerator Facility, Newport News, VA (United States); Ou, Longwu [Massachusetts Institute of Technology, Cambridge, MA (United States); Schmookler, Barack Abraham [Massachusetts Institute of Technology, Cambridge, MA (United States); Tennant, Christopher D. [Thomas Jefferson National Accelerator Facility, Newport News, VA (United States); Tschalar, C. [Massachusetts Institute of Technology, Cambridge, MA (United States); Williams, Gwyn P. [Thomas Jefferson National Accelerator Facility, Newport News, VA (United States); Zhang, Shukui [Thomas Jefferson National Accelerator Facility, Newport News, VA (United States)

    2013-11-01

    We report measurements of photon and neutron radiation levels observed while transmitting a 0.43 MW electron beam through millimeter-sized apertures and during beam-off, but accelerating gradient RF-on, operation. These measurements were conducted at the Free-Electron Laser (FEL) facility of the Jefferson National Accelerator Laboratory (JLab) using a 100 MeV electron beam from an energy-recovery linear accelerator. The beam was directed successively through 6 mm, 4 mm, and 2 mm diameter apertures of length 127 mm in aluminum at a maximum current of 4.3 mA (430 kW beam power). This study was conducted to characterize radiation levels for experiments that need to operate in this environment, such as the proposed DarkLight Experiment. We find that sustained transmission of a 430 kW continuous-wave (CW) beam through a 2 mm aperture is feasible with manageable beam-related backgrounds. We also find that during beam-off, RF-on operation, multipactoring inside the niobium cavities of the accelerator cryomodules is the primary source of ambient radiation when the machine is tuned for 130 MeV operation.

  1. Solving the Accelerator-Condenser Coupling Problem in a Nanosecond Dynamic Transmission Electron Microscope

    SciTech Connect (OSTI)

    Reed, B W; LaGrange, T; Shuttlesworth, R M; Gibson, D J; Campbell, G H; Browning, N D

    2009-12-29

    We describe a modification to a transmission electron microscope (TEM) that allows it to briefly (using a pulsed-laser-driven photocathode) operate at currents in excess of 10 mA while keeping the effects of condenser lens aberrations to a minimum. This modification allows real-space imaging of material microstructure with a resolution of order 10 nm over regions several {micro}m across with an exposure time of 15 ns. This is more than 6 orders of magnitude faster than typical video-rate TEM imaging. The key is the addition of a weak magnetic lens to couple the large-diameter high-current beam exiting the accelerator into the acceptance aperture of a conventional TEM condenser lens system. We show that the performance of the system is essentially consistent with models derived from ray tracing and finite element simulations. The instrument can also be operated as a conventional TEM by using the electron gun in a thermionic mode. The modification enables very high electron current densities in {micro}m-sized areas and could also be used in a non-pulsed system for high-throughput imaging and analytical TEM.

  2. Transmission electron microscopy of oxide dispersion strengthened (ODS) molybdenum: effects of irradiation on material microstructure

    SciTech Connect (OSTI)

    Baranwal, R. and Burke, M.G.

    2003-03-03

    Oxide dispersion strengthened (ODS) molybdenum has been characterized using transmission electron microscopy (TEM) to determine the effects of irradiation on material microstructure. This work describes the results-to-date from TEM characterization of unirradiated and irradiated ODS molybdenum. The general microstructure of the unirradiated material consists of fine molybdenum grains (< 5 {micro}m average grain size) with numerous low angle boundaries and isolated dislocation networks. 'Ribbon'-like lanthanum oxides are aligned along the working direction of the product form and are frequently associated with grain boundaries, serving to inhibit grain boundary and dislocation movement. In addition to the 'ribbons', discrete lanthanum oxide particles have also been detected. After irradiation, the material is characterized by the presence of nonuniformly distributed large ({approx} 20 to 100 nm in diameter), multi-faceted voids, while the molybdenum grain size and oxide morphology appear to be unaffected by irradiation.

  3. Dynamics of soft Nanomaterials captured by transmission electron microscopy in liquid water

    SciTech Connect (OSTI)

    Proetto, Maria T.; Rush, Anthony M.; Chien, Miao-Ping; Abellan Baeza, Patricia; Patterson, Joseph P.; Thompson, Matthew P.; Olson, Norman H.; Moore, Curtis E.; Rheingold, Arnold L.; Andolina, Christopher; Millstone, Jill; Howell, Stephen B.; Browning, Nigel D.; Evans, James E.; Gianneschi, Nathan C.

    2014-01-14

    In this paper we present in situ transmission electron microscopy (TEM) of soft, synthetic nanoparticles with a comparative analysis using conventional TEM methods. This comparison is made with the simple aim of describing what is an unprecedented example of in situ imaging by TEM. However, we contend the technique will quickly become essential in the characterization of analogous systems, especially where dynamics are of interest in the solvated state. In this case, particles were studied which were obtained from the direct polymerization of an oxaliplatin analog, designed for an ongoing program in novel chemotherapeutic delivery systems. The resulting nanoparticles provided sufficient contrast for facile imaging in situ, and point toward key design parameters that enable this new characterization approach for organic nanomaterials. We describe the preparation of the synthetic micellar nanoparticles to- gether with their characterization in liquid water.

  4. High resolution transmission electron microscopic in-situ observations of plastic deformation of compressed nanocrystalline gold

    SciTech Connect (OSTI)

    Wang, Guoyong; Lian, Jianshe; Jiang, Qing; Sun, Sheng; Zhang, Tong-Yi

    2014-09-14

    Nanocrystalline (nc) metals possess extremely high strength, while their capability to deform plastically has been debated for decades. Low ductility has hitherto been considered an intrinsic behavior for most nc metals, due to the lack of five independent slip systems actively operating during deformation in each nanograin. Here we report in situ high resolution transmission electron microscopic (HRTEM) observations of deformation process of nc gold under compression, showing the excellent ductility of individual and aggregate nanograins. Compression causes permanent change in the profile of individual nanograins, which is mediated by dislocation slip and grain rotation. The high rate of grain boundary sliding and large extent of widely exited grain rotation may meet the boundary compatibility requirements during plastic deformation. The in situ HRTEM observations suggest that nc gold is not intrinsically brittle under compressive loading.

  5. Unraveling irradiation induced grain growth with in situ transmission electron microscopy and coordinated modeling

    SciTech Connect (OSTI)

    Bufford, D. C.; Abdeljawad, F. F.; Foiles, S. M.; Hattar, K.

    2015-11-09

    Nanostructuring has been proposed as a method to enhance radiation tolerance, but many metallic systems are rejected due to significant concerns regarding long term grain boundary and interface stability. This work utilized recent advancements in transmission electron microscopy (TEM) to quantitatively characterize the grain size, texture, and individual grain boundary character in a nanocrystalline gold model system before and after in situ TEM ion irradiation with 10 MeV Si. The initial experimental measurements were fed into a mesoscale phase field model, which incorporates the role of irradiation-induced thermal events on boundary properties, to directly compare the observed and simulated grain growth with varied parameters. The observed microstructure evolution deviated subtly from previously reported normal grain growth in which some boundaries remained essentially static. In broader terms, the combined experimental and modeling techniques presented herein provide future avenues to enhance quantification and prediction of the thermal, mechanical, or radiation stability of grain boundaries in nanostructured crystalline systems.

  6. Rendering graphene supports hydrophilic with non-covalent aromatic functionalization for transmission electron microscopy

    SciTech Connect (OSTI)

    Pantelic, Radosav S., E-mail: pantelic@imbb.forth.gr [National Cancer Institute, 50 South Drive, Building 50, Room 4306, Bethesda, Maryland 20892 (United States); Fu, Wangyang; Schoenenberger, Christian [Department of Physics, University of Basel, Klingelbergstrasse 82, Basel CH-4056 (Switzerland); Stahlberg, Henning [Center for Cellular Imaging and NanoAnalytics, Biozentrum, University of Basel, Mattenstrasse 26, WRO-1058, Basel CH-4058 (Switzerland)

    2014-03-31

    Amorphous carbon films have been routinely used to enhance the preparation of frozen-hydrated samples for transmission electron microscopy (TEM), either in retaining protein concentration, providing mechanical stability or dissipating sample charge. However, strong background signal from the amorphous carbon support obstructs that of the sample, and the insulating properties of thin amorphous carbon films preclude any efficiency in dispersing charge. Graphene addresses the limitations of amorphous carbon. Graphene is a crystalline material with virtually no phase or amplitude contrast and unparalleled, high electrical carrier mobility. However, the hydrophobic properties of graphene have prevented its routine application in Cryo-TEM. This Letter reports a method for rendering graphene TEM supports hydrophilica convenient approach maintaining graphene's structural and electrical properties based on non-covalent, aromatic functionalization.

  7. Contribution of charge-transfer processes to ion-induced electron emission

    SciTech Connect (OSTI)

    Roesler, M.

    1996-12-01

    Charge changing events of ions moving inside metals are shown to contribute significantly to electron emission in the intermediate velocity regime via electrons coming from projectile ionization. Inclusion of equilibrium charge state fractions, together with two-electron Auger processes and resonant-coherent electron loss from the projectile, results in reasonable agreement with previous calculations for frozen protons, though a significant part of the emission is now interpreted in terms of charge exchange. The quantal character of the surface barrier transmission is shown to play an important role. The theory compares well with experimental observations for {ital H} projectiles. {copyright} {ital 1996 The American Physical Society.}

  8. The transfer between electron bulk kinetic energy and thermal energy in collisionless magnetic reconnection

    SciTech Connect (OSTI)

    Lu, San; Lu, Quanming; Huang, Can; Wang, Shui

    2013-06-15

    By performing two-dimensional particle-in-cell simulations, we investigate the transfer between electron bulk kinetic and electron thermal energy in collisionless magnetic reconnection. In the vicinity of the X line, the electron bulk kinetic energy density is much larger than the electron thermal energy density. The evolution of the electron bulk kinetic energy is mainly determined by the work done by the electric field force and electron pressure gradient force. The work done by the electron gradient pressure force in the vicinity of the X line is changed to the electron enthalpy flux. In the magnetic island, the electron enthalpy flux is transferred to the electron thermal energy due to the compressibility of the plasma in the magnetic island. The compression of the plasma in the magnetic island is the consequence of the electromagnetic force acting on the plasma as the magnetic field lines release their tension after being reconnected. Therefore, we can observe that in the magnetic island the electron thermal energy density is much larger than the electron bulk kinetic energy density.

  9. Development of a Silicon Based Electron Beam Transmission Window for Use in a KrF Excimer Laser System

    SciTech Connect (OSTI)

    C.A. Gentile; H.M. Fan; J.W. Hartfield; R.J. Hawryluk; F. Hegeler; P.J. Heitzenroeder; C.H. Jun; L.P. Ku; P.H. LaMarche; M.C. Myers; J.J. Parker; R.F. Parsells; M. Payen; S. Raftopoulos; J.D. Sethian

    2002-11-21

    The Princeton Plasma Physics Laboratory (PPPL), in collaboration with the Naval Research Laboratory (NRL), is currently investigating various novel materials (single crystal silicon, <100>, <110> and <111>) for use as electron-beam transmission windows in a KrF excimer laser system. The primary function of the window is to isolate the active medium (excimer gas) from the excitation mechanism (field-emission diodes). Chosen window geometry must accommodate electron energy transfer greater than 80% (750 keV), while maintaining structural integrity during mechanical load (1.3 to 2.0 atm base pressure differential, approximate 0.5 atm cyclic pressure amplitude, 5 Hz repetition rate) and thermal load across the entire hibachi area (approximate 0.9 W {center_dot} cm superscript ''-2''). In addition, the window must be chemically resistant to attack by fluorine free-radicals (hydrofluoric acid, secondary). In accordance with these structural, functional, and operational parameters, a 22.4 mm square silicon prototype window, coated with 500 nm thin-film silicon nitride (Si{sub 3}N{sub 4}), has been fabricated. The window consists of 81 square panes with a thickness of 0.019 mm {+-} 0.001 mm. Stiffened (orthogonal) sections are 0.065 mm in width and 0.500 mm thick (approximate). Appended drawing (Figure 1) depicts the window configuration. Assessment of silicon (and silicon nitride) material properties and CAD modeling and analysis of the window design suggest that silicon may be a viable solution to inherent parameters and constraints.

  10. Activators generated by electron transfer for atom transfer radical polymerization of styrene in the presence of mesoporous silica nanoparticles

    SciTech Connect (OSTI)

    Khezri, Khezrollah; Roghani-Mamaqani, Hossein

    2014-11-15

    Graphical abstract: Effect of mesoporous silica nanoparticles (MCM-41) on the activator generated by electron transfer for atom transfer radical polymerization (AGET ATRP) is investigated. Decrement of conversion and number average molecular weight and also increment of polydispersity index (PDI) values are three main results of addition of MCM-41 nanoparticles. Incorporation of MCM-41 nanoparticles in the polystyrene matrix can clearly increase thermal stability and decrease glass transition temperature of the nanocomposites. - Highlights: • Spherical morphology, hexagonal structure, and high surface area with regular pore diameters of the synthesized MCM-41 nanoparticles are examined. • AGET ATRP of styrene in the presence of MCM-41 nanoparticles is performed. • Effect of MCM-41 nanoparticles addition on the polymerization rate, conversion and molecular weights of the products are discussed. • Improvement in thermal stability of the nanocomposites and decreasing T{sub g} values was also observed by incorporation of MCM-41 nanoparticles. - Abstract: Activator generated by electron transfer for atom transfer radical polymerization was employed to synthesize well-defined mesoporous silica nanoparticles/polystyrene composites. Inherent features of spherical mesoporous silica nanoparticles were evaluated by nitrogen adsorption/desorption isotherm, X-ray diffraction and scanning electron microscopy analysis techniques. Conversion and molecular weight evaluations were carried out using gas and size exclusion chromatography respectively. By the addition of only 3 wt% mesoporous silica nanoparticles, conversion decreases from 81 to 58%. Similarly, number average molecular weight decreases from 17,116 to 12,798 g mol{sup −1}. However, polydispersity index (PDI) values increases from 1.24 to 1.58. A peak around 4.1–4.2 ppm at proton nuclear magnetic resonance spectroscopy results clearly confirms the living nature of the polymerization. Thermogravimetric

  11. Lithium electrodeposition dynamics in aprotic electrolyte observed in situ via transmission electron microscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Leenheer, Andrew Jay; Jungjohann, Katherine Leigh; Zavadil, Kevin Robert; Sullivan, John P.; Harris, Charles Thomas

    2015-03-18

    Electrodeposited metallic lithium is an ideal negative battery electrode, but nonuniform microstructure evolution during cycling leads to degradation and safety issues. A better understanding of the Li plating and stripping processes is needed to enable practical Li-metal batteries. Here we use a custom microfabricated, sealed liquid cell for in situ scanning transmission electron microscopy (STEM) to image the first few cycles of lithium electrodeposition/dissolution in liquid aprotic electrolyte at submicron resolution. Cycling at current densities from 1 to 25 mA/cm2 leads to variations in grain structure, with higher current densities giving a more needle-like, higher surface area deposit. The effectmore » of the electron beam was explored, and it was found that, even with minimal beam exposure, beam-induced surface film formation could alter the Li microstructure. The electrochemical dissolution was seen to initiate from isolated points on grains rather than uniformly across the Li surface, due to the stabilizing solid electrolyte interphase surface film. As a result, we discuss the implications for operando STEM liquid-cell imaging and Li-battery applications.« less

  12. An efficient and cost-effective method for preparing transmission electron microscopy samples from powders

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Wen, Haiming; Lin, Yaojun; Seidman, David N.; Schoenung, Julie M.; van Rooyen, Isabella J.; Lavernia, Enrique J.

    2015-09-09

    The preparation of transmission electron microcopy (TEM) samples from powders with particle sizes larger than ~100 nm poses a challenge. The existing methods are complicated and expensive, or have a low probability of success. Herein, we report a modified methodology for preparation of TEM samples from powders, which is efficient, cost-effective, and easy to perform. This method involves mixing powders with an epoxy on a piece of weighing paper, curing the powder–epoxy mixture to form a bulk material, grinding the bulk to obtain a thin foil, punching TEM discs from the foil, dimpling the discs, and ion milling the dimpledmore » discs to electron transparency. Compared with the well established and robust grinding–dimpling–ion-milling method for TEM sample preparation for bulk materials, our modified approach for preparing TEM samples from powders only requires two additional simple steps. In this article, step-by-step procedures for our methodology are described in detail, and important strategies to ensure success are elucidated. Furthermore, our methodology has been applied successfully for preparing TEM samples with large thin areas and high quality for many different mechanically milled metallic powders.« less

  13. Defects in paramagnetic Co-doped ZnO films studied by transmission electron microscopy

    SciTech Connect (OSTI)

    Kovcs, A.; Duchamp, M.; Boothroyd, C. B.; Dunin-Borkowski, R. E.; Ney, A.; Ney, V.; Galindo, P. L.; Kaspar, T. C.; Chambers, S. A.

    2013-12-28

    We study planar defects in epitaxial Co:ZnO dilute magnetic semiconductor thin films deposited on c-plane sapphire (Al{sub 2}O{sub 3}), as well as the Co:ZnO/Al{sub 2}O{sub 3} interface, using aberration-corrected transmission electron microscopy and electron energy-loss spectroscopy. Co:ZnO samples that were deposited using pulsed laser deposition and reactive magnetron sputtering are both found to contain extrinsic stacking faults, incoherent interface structures, and compositional variations within the first 34 Co:ZnO layers next to the Al{sub 2}O{sub 3} substrate. The stacking fault density is in the range of 10{sup 17} cm{sup ?3}. We also measure the local lattice distortions around the stacking faults. It is shown that despite the relatively high density of planar defects, lattice distortions, and small compositional variation, the Co:ZnO films retain paramagnetic properties.

  14. Probing the dependence of electron transfer on size and coverage in carbon nanotube-quantum dot heterostructures

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Wang, Lei; Wong, Stanislaus S.; Han, Jinkyu; Zhu, Yuqi; Jaye, Cherno; Liu, Haiqing; Li, Zhuo -Qun; Taylor, Gordon T.; Fischer, Daniel A.; Appenzeller, Joerg; et al

    2015-11-16

    As a model system for understanding charge transfer in novel architectural designs for solar cells, double-walled carbon nanotube (DWNT)–CdSe quantum dot (QD) (QDs with average diameters of 2.3, 3.0, and 4.1 nm) heterostructures have been fabricated. The individual nanoscale building blocks were successfully attached and combined using a hole-trapping thiol linker molecule, i.e., 4-mercaptophenol (MTH), through a facile, noncovalent π–π stacking attachment strategy. Transmission electron microscopy confirmed the attachment of QDs onto the external surfaces of the DWNTs. We herein demonstrate a meaningful and unique combination of near-edge X-ray absorption fine structure (NEXAFS) and Raman spectroscopies bolstered by complementary electricalmore » transport measurements in order to elucidate the synergistic interactions between CdSe QDs and DWNTs, which are facilitated by the bridging MTH molecules that can scavenge photoinduced holes and potentially mediate electron redistribution between the conduction bands in CdSe QDs and the C 2p-derived states of the DWNTs. Specifically, we correlated evidence of charge transfer as manifested by (i) changes in the NEXAFS intensities of π* resonance in the C K-edge and Cd M3-edge spectra, (ii) a perceptible outer tube G-band downshift in frequency in Raman spectra, as well as (iii) alterations in the threshold characteristics present in transport data as a function of CdSe QD deposition onto the DWNT surface. Furthermore, the separate effects of (i) varying QD sizes and (ii) QD coverage densities on the electron transfer were independently studied.« less

  15. Probing the dependence of electron transfer on size and coverage in carbon nanotube-quantum dot heterostructures

    SciTech Connect (OSTI)

    Wang, Lei; Wong, Stanislaus S.; Han, Jinkyu; Zhu, Yuqi; Jaye, Cherno; Liu, Haiqing; Li, Zhuo -Qun; Taylor, Gordon T.; Fischer, Daniel A.; Appenzeller, Joerg; Zhu, Ruiping

    2015-11-16

    As a model system for understanding charge transfer in novel architectural designs for solar cells, double-walled carbon nanotube (DWNT)–CdSe quantum dot (QD) (QDs with average diameters of 2.3, 3.0, and 4.1 nm) heterostructures have been fabricated. The individual nanoscale building blocks were successfully attached and combined using a hole-trapping thiol linker molecule, i.e., 4-mercaptophenol (MTH), through a facile, noncovalent π–π stacking attachment strategy. Transmission electron microscopy confirmed the attachment of QDs onto the external surfaces of the DWNTs. We herein demonstrate a meaningful and unique combination of near-edge X-ray absorption fine structure (NEXAFS) and Raman spectroscopies bolstered by complementary electrical transport measurements in order to elucidate the synergistic interactions between CdSe QDs and DWNTs, which are facilitated by the bridging MTH molecules that can scavenge photoinduced holes and potentially mediate electron redistribution between the conduction bands in CdSe QDs and the C 2p-derived states of the DWNTs. Specifically, we correlated evidence of charge transfer as manifested by (i) changes in the NEXAFS intensities of π* resonance in the C K-edge and Cd M3-edge spectra, (ii) a perceptible outer tube G-band downshift in frequency in Raman spectra, as well as (iii) alterations in the threshold characteristics present in transport data as a function of CdSe QD deposition onto the DWNT surface. Furthermore, the separate effects of (i) varying QD sizes and (ii) QD coverage densities on the electron transfer were independently studied.

  16. Convective Heat Transfer Coefficients of Automatic Transmission Fluid Jets with Implications for Electric Machine Thermal Management: Preprint

    SciTech Connect (OSTI)

    Bennion, Kevin; Moreno, Gilberto

    2015-09-29

    Thermal management for electric machines (motors/ generators) is important as the automotive industry continues to transition to more electrically dominant vehicle propulsion systems. Cooling of the electric machine(s) in some electric vehicle traction drive applications is accomplished by impinging automatic transmission fluid (ATF) jets onto the machine's copper windings. In this study, we provide the results of experiments characterizing the thermal performance of ATF jets on surfaces representative of windings, using Ford's Mercon LV ATF. Experiments were carried out at various ATF temperatures and jet velocities to quantify the influence of these parameters on heat transfer coefficients. Fluid temperatures were varied from 50 degrees C to 90 degrees C to encompass potential operating temperatures within an automotive transaxle environment. The jet nozzle velocities were varied from 0.5 to 10 m/s. The experimental ATF heat transfer coefficient results provided in this report are a useful resource for understanding factors that influence the performance of ATF-based cooling systems for electric machines.

  17. Impact of membrane-induced particle immobilization on seeded growth monitored by in situ liquid scanning transmission electron microscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Weiner, Rebecca G.; Chen, Dennis P.; Unocic, Raymond R.; Skrabalak, Sara E.

    2016-04-01

    In situ liquid cell scanning transmission electron microscopy probes seeded growth in real time. The growth of Pd on Au nanocubes is monitored as a model system to compare growth within a liquid cell and traditional colloidal synthesis. Furthermore, different growth patterns are observed due to seed immobilization and the highly reducing environment within the liquid cell.

  18. Real-time studies of battery electrochemical reactions inside a transmission electron microscope.

    SciTech Connect (OSTI)

    Leung, Kevin; Hudak, Nicholas S.; Liu, Yang; Liu, Xiaohua H.; Fan, Hongyou; Subramanian, Arunkumar; Shaw, Michael J.; Sullivan, John Patrick; Huang, Jian Yu

    2012-01-01

    We report the development of new experimental capabilities and ab initio modeling for real-time studies of Li-ion battery electrochemical reactions. We developed three capabilities for in-situ transmission electron microscopy (TEM) studies: a capability that uses a nanomanipulator inside the TEM to assemble electrochemical cells with ionic liquid or solid state electrolytes, a capability that uses on-chip assembly of battery components on to TEM-compatible multi-electrode arrays, and a capability that uses a TEM-compatible sealed electrochemical cell that we developed for performing in-situ TEM using volatile battery electrolytes. These capabilities were used to understand lithiation mechanisms in nanoscale battery materials, including SnO{sub 2}, Si, Ge, Al, ZnO, and MnO{sub 2}. The modeling approaches used ab initio molecular dynamics to understand early stages of ethylene carbonate reduction on lithiated-graphite and lithium surfaces and constrained density functional theory to understand ethylene carbonate reduction on passivated electrode surfaces.

  19. High resolution transmission electron microscopy of melamine-formaldehyde aerogels and silica aerogels

    SciTech Connect (OSTI)

    Ruben, G.C. (Dartmouth Coll., Hanover, NH (United States). Dept. of Biological Sciences)

    1991-09-01

    The goal of the high resolution transmission electron microscopy (HRTEM) was to image the structure of two tetramethyl orthosilicate (TMOS) and two melamine-formaldehyde (MF) aerogels at the single polymer chain level{sup 1,2}. With this level of structural resolution we hoped to interrelate each aerogel's structure with its physical properties and its method of synthesis. Conventional single-step base catalysed TMOS aerogels show strings of spheroidal particles linked together with minimal necking. The spheroidal particles range from 86--132 {Angstrom} and average 113{plus minus}10 {Angstrom} in diameter{sup 2}. In contrast the TMOS aerogels reported on here were made by a two step method. After extended silica chains are grown in solution under acidic conditions with a substoichiometric amount of water, the reaction is stopped and the methanol hydrolysed from TMOS is removed. Then base catalysis and additional water are added to cause gel formation is a nonalcoholic solvent. The MF aerogels were prepared for HRTEM by fracturing them on a stereo microscope stage with razor knife so that fractured pieces with smooth flat surfaces could be selected for platinum-carbon replication. The two silica (TMOS) aerogels were both transparent and difficult to see. These aerogels were fractured on a stereo microscope stage with tweezers. 6 refs., 4 figs.

  20. Powering microbes with electricity: direct electron transfer from electrodes to microbes

    SciTech Connect (OSTI)

    Lovley, DR

    2010-09-16

    P>The discovery of electrotrophs, microorganisms that can directly accept electrons from electrodes for the reduction of terminal electron acceptors, has spurred the investigation of a wide range of potential applications. To date, only a handful of pure cultures have been shown to be capable of electrotrophy, but this process has also been inferred in many studies with undefined consortia. Potential electron acceptors include: carbon dioxide, nitrate, metals, chlorinated compounds, organic acids, protons and oxygen. Direct electron transfer from electrodes to cells has many advantages over indirect electrical stimulation of microbial metabolism via electron shuttles or hydrogen production. Supplying electrons with electrodes for the bioremediation of chlorinated compounds, nitrate or toxic metals may be preferable to adding organic electron donors or hydrogen to the subsurface or bioreactors. The most transformative application of electrotrophy may be microbial electrosynthesis in which carbon dioxide and water are converted to multi-carbon organic compounds that are released extracellularly. Coupling photovoltaic technology with microbial electrosynthesis represents a novel photosynthesis strategy that avoids many of the drawbacks of biomass-based strategies for the production of transportation fuels and other organic chemicals. The mechanisms for direct electron transfer from electrodes to microorganisms warrant further investigation in order to optimize envisioned applications.

  1. Evidence for decoupled electron and proton transfer in the electrochemical oxidation of ammonia on Pt(100)

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Katsounaros, Ioannis; Chen, Ting; Gewirth, Andrew A.; Markovic, Nenad M.; Koper, Marc T. M.

    2016-01-12

    The two traditional mechanisms of the electrochemical ammonia oxidation consider only concerted proton-electron transfer elementary steps and thus they predict that the rate–potential relationship is independent of the pH on the pH-corrected RHE potential scale. In this letter we show that this is not the case: the increase of the solution pH shifts the onset of the NH3-to-N2 oxidation on Pt(100) to lower potentials and also leads to higher surface concentration of formed NOad before the latter is oxidized to nitrite. Therefore, we present a new mechanism for the ammonia oxidation which incorporates a deprotonation step occurring prior to themore » electron transfer. The deprotonation step yields a negatively charged surface-adsorbed species which is discharged in a subsequent electron transfer step before the N–N bond formation. The negatively charged species is thus a precursor for the formation of N2 and NO. The new mechanism should be a future guide for computational studies aiming at the identification of intermediates and corresponding activation barriers for the elementary steps. As a result, ammonia oxidation is a new example of a bond-forming reaction on (100) terraces which involves decoupled proton-electron transfer.« less

  2. Stability of vacuum-ultraviolet radiometric transfer standards: Electron cyclotron resonance versus hollow cathode source

    SciTech Connect (OSTI)

    Gottwald, Alexander; Richter, Mathias; Ulm, Gerhard; Schuehle, Udo

    2005-02-01

    Established transfer standards such as Penning and hollow cathode discharge sources suffer from limited spectral range and, in particular, a limited lifetime and stability due to electrode erosion. The development of a vacuum-ultraviolet radiation source based on an electron cyclotron resonance (ECR)-created plasma might overcome these limitations. To test such a source with regard to its usefulness as radiometric transfer standard, the emission intensity of a Ne plasma was monitored over an operation period of 180 days, with regard to stability and reproducibility in the 50-75 nm wavelength range. For comparison and calibration, a hollow cathode was used as transfer standard traceable to the electron storage ring BESSY II as primary standard. It was found that the ECR source exceeded the lifetime of the hollow cathode source by far, offering a more balanced spectral emission line variety with similar stability.

  3. Transmission electron microscopic study of pyrochlore to defect-fluorite transition in rare-earth pyrohafnates

    SciTech Connect (OSTI)

    Karthik, Chinnathambi; Center for Advanced Energy Studies, 995 University Blvd, Idaho Falls, ID 83415 ; Anderson, Thomas J.; Gout, Delphine; Ubic, Rick; Center for Advanced Energy Studies, 995 University Blvd, Idaho Falls, ID 83415

    2012-10-15

    A structural transition in rare earth pyrohafnates, Ln{sub 2}Hf{sub 2}O{sub 7} (Ln=Y, La, Pr, Nd, Tb, Dy, Yb and Lu), has been identified. Neutron diffraction showed that the structure transforms from well-ordered pyrochloric to fully fluoritic through the lanthanide series from La to Lu with a corresponding increase in the position parameter x of the 48f (Fd3{sup Macron }m) oxygen site from 0.330 to 0.375. As evidenced by the selected area electron diffraction, La{sub 2}Hf{sub 2}O{sub 7}, Pr{sub 2}Hf{sub 2}O{sub 7} and Nd{sub 2}Hf{sub 2}O{sub 7} exhibited a well-ordered pyrocholoric structure with the presence of intense superlattice spots, which became weak and diffuse (in Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}) before disappearing completely as the series progressed towards the Lu end. High resolution electron microscopic studies showed the breakdown of the pyrochlore ordering in the form of antiphase domains resulting in diffused smoke-like superlattice spots in the case of Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}. - Graphical abstract: Transmission electron microscopic studies showed the ordered pyrochlore to defect fluorite transition in rare-earth pyrohafnates to occur via the formation of anti-phase domains to start with. Highlights: Black-Right-Pointing-Pointer Pyrochlore to fluorite structural transition in rare earth pyrohafnates. Black-Right-Pointing-Pointer La{sub 2}Hf{sub 2}O{sub 7}, Pr{sub 2}Hf{sub 2}O{sub 7} and Nd{sub 2}Hf{sub 2}O{sub 7} showed well ordered pyrochlore structure. Black-Right-Pointing-Pointer Short range ordering in Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}. Black-Right-Pointing-Pointer Break down of pyrochlore ordering due to antiphase boundaries. Black-Right-Pointing-Pointer Rest of the series showed fluoritic structure.

  4. Constraint-Based Modeling of Carbon Fixation and the Energetics of Electron Transfer in Geobacter metallireducens

    SciTech Connect (OSTI)

    Feist, AM; Nagarajan, H; Rotaru, AE; Tremblay, PL; Zhang, T; Nevin, KP; Lovley, DR; Zengler, K

    2014-04-24

    Geobacter species are of great interest for environmental and biotechnology applications as they can carry out direct electron transfer to insoluble metals or other microorganisms and have the ability to assimilate inorganic carbon. Here, we report on the capability and key enabling metabolic machinery of Geobacter metallireducens GS-15 to carry out CO2 fixation and direct electron transfer to iron. An updated metabolic reconstruction was generated, growth screens on targeted conditions of interest were performed, and constraint-based analysis was utilized to characterize and evaluate critical pathways and reactions in G. metallireducens. The novel capability of G. metallireducens to grow autotrophically with formate and Fe(III) was predicted and subsequently validated in vivo. Additionally, the energetic cost of transferring electrons to an external electron acceptor was determined through analysis of growth experiments carried out using three different electron acceptors (Fe(III), nitrate, and fumarate) by systematically isolating and examining different parts of the electron transport chain. The updated reconstruction will serve as a knowledgebase for understanding and engineering Geobacter and similar species. Author Summary The ability of microorganisms to exchange electrons directly with their environment has large implications for our knowledge of industrial and environmental processes. For decades, it has been known that microbes can use electrodes as electron acceptors in microbial fuel cell settings. Geobacter metallireducens has been one of the model organisms for characterizing microbe-electrode interactions as well as environmental processes such as bioremediation. Here, we significantly expand the knowledge of metabolism and energetics of this model organism by employing constraint-based metabolic modeling. Through this analysis, we build the metabolic pathways necessary for carbon fixation, a desirable property for industrial chemical production. We

  5. Theory of ultrafast photoinduced electron transfer from a bulk semiconductor to a quantum dot

    SciTech Connect (OSTI)

    Rasmussen, Andrew M. Ramakrishna, S.; Weiss, Emily A.; Seideman, Tamar

    2014-04-14

    This paper describes analytical and numerical results from a model Hamiltonian method applied to electron transfer (ET) from a quasicontinuum (QC) of states to a set of discrete states, with and without a mediating bridge. Analysis of the factors that determine ET dynamics yields guidelines for achieving high-yield electron transfer in these systems, desired for instance for applications in heterogeneous catalysis. These include the choice of parameters of the laser pulse that excites the initial state into a continuum electronic wavepacket and the design of the coupling between the bridge molecule and the donor and acceptor. The vibrational mode on a bridging molecule between donor and acceptor has an influence on the yield of electron transfer via Franck-Condon factors, even in cases where excited vibrational states are only transiently populated. Laser-induced coherence of the initial state as well as energetic overlap is crucial in determining the ET yield from a QC to a discrete state, whereas the ET time is influenced by competing factors from the coupling strength and the coherence properties of the electronic wavepacket.

  6. Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications

    SciTech Connect (OSTI)

    Warren, Jeffrey J.; Tronic, Tristan A.; Mayer, James M.

    2010-12-08

    Many, if not most, redox reactions are coupled to proton transfers. This includes most common sources of chemical potential energy, from the bioenergetic processes that power cells to the fossil fuel combustion that powers cars. These proton-coupled electron transfer or PCET processes may involve multiple electrons and multiple protons, as in the 4 e, 4 H+ reduction of dioxygen (O2) to water (eq 1), or can involve one electron and one proton such as the formation of tyrosyl radicals from tyrosine residues (TyrOH) in enzymatic catalytic cycles (eq 2). In addition, many multi-electron, multi-proton processes proceed in one-electron and one-proton steps. Organic reactions that proceed in one-electron steps involve radical intermediates, which play critical roles in a wide range of chemical, biological, and industrial processes. This broad and diverse class of PCET reactions are central to a great many chemical and biochemical processes, from biological catalysis and energy transduction, to bulk industrial chemical processes, to new approaches to solar energy conversion. PCET is therefore of broad and increasing interest, as illustrated by this issue and a number of other recent reviews.

  7. Picosecond electron transfer in diporphyrin models of Photosystem II of green plants

    SciTech Connect (OSTI)

    Netzel, T L; Fujita, I; Wang, C B; Fajer, J

    1980-01-01

    Green plants and photosynthetic bacteria efficiently transform the energy of an absorbed photon into redox products. Current in vivo and in vitro studies on Photosystem II (PS II) suggest the electron donor is a chlorophyll monomer, ligated to produce the high oxidation potential of P680, and the electron acceptor is pheophytin, a metal-free chlorophyll. This study probes the behavior of this PS II model in solvents of high dielectric constant and tests the sensitivity of its charge transfer reactions to increases in linking chain length as well as to changes in the relative orientation of the porphyrin subunits. (ACR)

  8. Quantum DotBridgeFullerene Heterodimers with Controlled Photoinduced Electron Transfer

    SciTech Connect (OSTI)

    Cotlet, M.; Xu, Z.

    2011-06-27

    A series of donor-bridge-acceptor systems in the form of core/shell CdSe/ZnS quantum dot-bridge-fullerene heterodimers (see picture) with varying bridge length and varying quantum dot size were self-assembled by a surface-based stepwise method to demonstrate control of the rate and of the magnitude of fluctuations of photoinduced electron transfer at the single-molecule level.

  9. OSTIblog Articles in the electron transfer reactions Topic | OSTI, US Dept

    Office of Scientific and Technical Information (OSTI)

    of Energy Office of Scientific and Technical Information electron transfer reactions Topic Celebrating the 20th Anniversary of Nobel Prizes for Two DOE-associated Researchers by Mary Schorn 05 Oct, 2012 in Science Communications 4261 AccompDOEnobels_slide.jpg Celebrating the 20th Anniversary of Nobel Prizes for Two DOE-associated Researchers Read more about 4261 DOE-associated researchers have contributed to the advancement of a variety of science disciplines as a result of research they

  10. Metal complex-based electron-transfer mediators in dye-sensitized solar cells

    DOE Patents [OSTI]

    Elliott, C. Michael; Sapp, Shawn A.; Bignozzi, Carlo Alberto; Contado, Cristiano; Caramori, Stefano

    2006-03-28

    This present invention provides a metal-ligand complex and methods for using and preparing the same. In particular, the metal-ligand complex of the present invention is of the formula: L.sub.a-M-X.sub.b where L, M, X, a, and b are those define herein. The metal-ligand complexes of the present invention are useful in a variety of applications including as electron-transfer mediators in dye-sensitized solar cells and related photoelectrochromic devices.

  11. An efficient implementation of the localized operator partitioning method for electronic energy transfer

    SciTech Connect (OSTI)

    Nagesh, Jayashree; Brumer, Paul; Izmaylov, Artur F.

    2015-02-28

    The localized operator partitioning method [Y. Khan and P. Brumer, J. Chem. Phys. 137, 194112 (2012)] rigorously defines the electronic energy on any subsystem within a molecule and gives a precise meaning to the subsystem ground and excited electronic energies, which is crucial for investigating electronic energy transfer from first principles. However, an efficient implementation of this approach has been hindered by complicated one- and two-electron integrals arising in its formulation. Using a resolution of the identity in the definition of partitioning, we reformulate the method in a computationally efficient manner that involves standard one- and two-electron integrals. We apply the developed algorithm to the 9 − ((1 − naphthyl) − methyl) − anthracene (A1N) molecule by partitioning A1N into anthracenyl and CH{sub 2} − naphthyl groups as subsystems and examine their electronic energies and populations for several excited states using configuration interaction singles method. The implemented approach shows a wide variety of different behaviors amongst the excited electronic states.

  12. Regulation of electron transfer processes affects phototrophic mat structure and activity

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Ha, Phuc T.; Renslow, Ryan S.; Atci, Erhan; Reardon, Patrick N.; Lindemann, Stephen R.; Fredrickson, James K.; Call, Douglas R.; Beyenal, Haluk

    2015-09-03

    Phototrophic microbial mats are among the most diverse ecosystems in nature. These systems undergo daily cycles in redox potential caused by variations in light energy input and metabolic interactions among the microbial species. In this work, solid electrodes with controlled potentials were placed under mats to study the electron transfer processes between the electrode and the microbial mat. The phototrophic microbial mat was harvested from Hot Lake, a hypersaline, epsomitic lake located near Oroville (Washington, USA). We operated two reactors: graphite electrodes were polarized at potentials of -700 mVAg/AgCl [cathodic (CAT) mat system] and +300 mVAg/AgCl [anodic (AN) mat system]more » and the electron transfer rates between the electrode and mat were monitored. We observed a diel cycle of electron transfer rates for both AN and CAT mat systems. Interestingly, the CAT mats generated the highest reducing current at the same time points that the AN mats showed the highest oxidizing current. To characterize the physicochemical factors influencing electron transfer processes, we measured depth profiles of dissolved oxygen (DO) and sulfide in the mats using microelectrodes. We further demonstrated that the mat-to-electrode and electrode-to-mat electron transfer rates were light- and temperature-dependent. Using nuclear magnetic resonance (NMR) imaging, we determined that the electrode potential regulated the diffusivity and porosity of the microbial mats. Both porosity and diffusivity were higher in the CAT mats than in the AN mats. We also used NMR spectroscopy for high-resolution quantitative metabolite analysis and found that the CAT mats had significantly higher concentrations of osmoprotectants such as betaine and trehalose. Subsequently, we performed amplicon sequencing across the V4 region of the 16S rRNA gene of incubated mats to understand the impact of electrode potential on microbial community structure. In conclusion, these data suggested that

  13. Structural evolution and strain induced mixing in Cu–Co composites studied by transmission electron microscopy and atom probe tomography

    SciTech Connect (OSTI)

    Bachmaier, A.; Aboulfadl, H.; Pfaff, M.; Mücklich, F.; Motz, C.

    2015-02-15

    A Cu–Co composite material is chosen as a model system to study structural evolution and phase formations during severe plastic deformation. The evolving microstructures as a function of the applied strain were characterized at the micro-, nano-, and atomic scale-levels by combining scanning electron microscopy and transmission electron microscopy including energy-filtered transmission electron microscopy and electron energy-loss spectroscopy. The amount of intermixing between the two phases at different strains was examined at the atomic scale using atom probe tomography as complimentary method. It is shown that Co particles are dissolved in the Cu matrix during severe plastic deformation to a remarkable extent and their size, number, and volume fraction were quantitatively determined during the deformation process. From the results, it can be concluded that supersaturated solid solutions up to 26 at.% Co in a fcc Cu–26 at.% Co alloy are obtained during deformation. However, the distribution of Co was found to be inhomogeneous even at the highest degree of investigated strain. - Highlights: • Structural evolution in a deformed Cu–Co composite is studied on all length scales. • Amount of intermixing is examined by atom-probe tomography. • Supersaturated solid solutions up to 26 at.% Co in Cu are observed.

  14. Electron transfer reactivity of the aqueous iron(IV)–oxo complex. Outer-sphere vs proton-coupled electron transfer

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

    2016-06-18

    Here, the kinetics of oxidation of organic and inorganic reductants by aqueous iron(IV) ions, FeIV(H2O)5O2+ (hereafter FeIVaqO2+), are reported. The substrates examined include several water-soluble ferrocenes, hexachloroiridate(III), polypyridyl complexes M(NN)32+ (M = Os, Fe and Ru; NN = phenanthroline, bipyridine and derivatives), HABTS–/ABTS2–, phenothiazines, CoII(dmgBF2)2, macrocyclic nickel(II) complexes, and aqueous cerium(III). Most of the reductants were oxidized cleanly to the corresponding one-electron oxidation products, with the exception of phenothiazines which produced the corresponding oxides in a single-step reaction, and polypyridyl complexes of Fe(II) and Ru(II) that generated ligand-modified products. FeIVaqO2+ oxidizes even Ce(III) (E0 in 1 M HClO4 = 1.7more » V) with a rate constant greater than 104 M–1 s–1. In 0.10 M aqueous HClO4 at 25 °C, the reactions of Os(phen)32+ (k = 2.5 × 105 M–1 s–1), IrCl63– (1.6 × 106), ABTS2– (4.7 × 107), and Fe(cp)(C5H4CH2OH) (6.4 × 107) appear to take place by outer sphere electron transfer (OSET). The rate constants for the oxidation of Os(phen)32+ and of ferrocenes remained unchanged in the acidity range 0.05 < [H+] < 0.10 M, ruling out prior protonation of FeIVaqO2+ and further supporting the OSET assignment. A fit to Marcus cross-relation yielded a composite parameter (log k22 + E0Fe/0.059) = 17.2 ± 0.8, where k22 and E0Fe are the self-exchange rate constant and reduction potential, respectively, for the FeIVaqO2+/FeIIIaqO+ couple. Comparison with literature work suggests k22 < 10–5 M–1 s–1 and thus E0(FeIVaqO2+/FeIIIaqO+) > 1.3 V. For proton-coupled electron transfer, the reduction potential is estimated at E0 (FeIVaqO2+, H+/FeIIIaqOH2+) ≥ 1.95 V.« less

  15. Proton-Coupled Electron Transfer in Molecular Electrocatalysis: Theoretical Methods and Design Principles

    SciTech Connect (OSTI)

    Solis, Brian H.; Hammes-Schiffer, Sharon

    2014-07-07

    Molecular electrocatalysts play an essential role in a wide range of energy conversion processes. The objective of electrocatalyst design is to maximize the turnover frequency and minimize the overpotential for the overall catalytic cycle. Typically the catalytic cycle is dominated by key proton-coupled electron transfer (PCET) processes comprised of sequential or concerted electron transfer and proton transfer steps. A variety of theoretical methods have been developed to investigate the mechanisms, thermodynamics, and kinetics of PCET processes in electrocatalytic cycles. Electronic structure methods can be used to calculate the reduction potentials and pKa’s and to generate thermodynamic schemes, free energy reaction pathways, and Pourbaix diagrams, which indicate the most stable species at each pH and potential. These types of calculations have assisted in identifying the thermodynamically favorable mechanisms under specified experimental conditions, such as acid strength and overpotential. Such calculations have also revealed linear correlations among the thermodynamic properties, which can be used to predict the impact of modifying the ligand, substituents, or metal center. The role of non-innocent ligands, namely ligand protonation or reduction, has also been examined theoretically. In addition, the rate constants for electron and proton transfer reactions, as well as concerted PCET reactions, have been calculated to investigate the kinetics of molecular electrocatalysts. The concerted PCET mechanism is thought to lower the overpotential required for catalysis by avoiding high-energy intermediates. Rate constant calculations have revealed that the concerted mechanism involving intramolecular proton transfer will be favored by designing more flexible ligands that facilitate the proton donor-acceptor motion while also maintaining a sufficiently short equilibrium proton donor-acceptor distance. Overall, theoretical methods have assisted in the interpretation

  16. Transfers

    Broader source: Energy.gov [DOE]

    Transfer means a change of an employee, from one Federal government branch (executive, legislative, judicial) to another or from one agency to another without a break in service of 1 full work day. 

  17. Room temperature, hybrid sodium-based flow batteries with multi-electron transfer redox reactions

    SciTech Connect (OSTI)

    Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; Sprenkle, Vincent L.

    2015-06-11

    We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volume of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multielectron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. Furthermore, the critical barriers to mature this new HNFBs have also been explored.

  18. Room Temperature, Hybrid Sodium-Based Flow Batteries with Multi-Electron Transfer Redox Reactions

    SciTech Connect (OSTI)

    Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; Sprenkle, Vincent L.

    2015-06-11

    We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volume of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multielectron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. The critical barriers to mature this new HNFBs have also been explored.

  19. Electronic and vibronic properties of a discotic liquid-crystal and its charge transfer complex

    SciTech Connect (OSTI)

    Haverkate, Lucas A.; Mulder, Fokko M.; Zbiri, Mohamed Johnson, Mark R.; Carter, Elizabeth; Kotlewski, Arek; Picken, S.

    2014-01-07

    Discotic liquid crystalline (DLC) charge transfer (CT) complexes combine visible light absorption and rapid charge transfer characteristics, being favorable properties for photovoltaic (PV) applications. We present a detailed study of the electronic and vibrational properties of the prototypic 1:1 mixture of discotic 2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6) and 2,4,7-trinitro-9-fluorenone (TNF). It is shown that intermolecular charge transfer occurs in the ground state of the complex: a charge delocalization of about 10{sup ?2} electron from the HAT6 core to TNF is deduced from both Raman and our previous NMR measurements [L. A. Haverkate, M. Zbiri, M. R. Johnson, B. Deme, H. J. M. de Groot, F. Lefeber, A. Kotlewski, S. J. Picken, F. M. Mulder, and G. J. Kearley, J. Phys. Chem. B 116, 13098 (2012)], implying the presence of permanent dipoles at the donor-acceptor interface. A combined analysis of density functional theory calculations, resonant Raman and UV-VIS absorption measurements indicate that fast relaxation occurs in the UV region due to intramolecular vibronic coupling of HAT6 quinoidal modes with lower lying electronic states. Relatively slower relaxation in the visible region the excited CT-band of the complex is also indicated, which likely involves motions of the TNF nitro groups. The fast quinoidal relaxation process in the hot UV band of HAT6 relates to pseudo-Jahn-Teller interactions in a single benzene unit, suggesting that the underlying vibronic coupling mechanism can be generic for polyaromatic hydrocarbons. Both the presence of ground state CT dipoles and relatively slow relaxation processes in the excited CT band can be relevant concerning the design of DLC based organic PV systems.

  20. Largely defocused probe scanning transmission electron microscopy for imaging local modulation of strain field in a hetero interface

    SciTech Connect (OSTI)

    Kim, Suhyun Jung, Younheum; Kim, Joong Jung; Lee, Sunyoung; Lee, Haebum; Oshima, Yoshifumi

    2014-10-13

    We present an innovative method for characterizing the strain field in three dimensions in a hetero interface. Largely defocused probe scanning transmission electron microscopy (LDP-STEM) was employed for imaging the inhomogeneous strain field in a germanium (Ge) layer deposited on a silicon (Si) substrate. In the LDP-STEM image, Ge-atomic columns that are relaxed or strained to the Si substrate in the Si/Ge hetero interface were observed to be distinguishable, allowing for the qualitative characterization of the coherency of the crystal growth. Our results revealed that the strain field is locally modulated along the in-plane direction in the Si/Ge hetero interface.

  1. In-situ optical transmission electron microscope study of exciton phonon replicas in ZnO nanowires by cathodoluminescence

    SciTech Connect (OSTI)

    Yang, Shize; Tian, Xuezeng; Wang, Lifen; Wei, Jiake; Qi, Kuo; Li, Xiaomin; Xu, Zhi E-mail: xdbai@iphy.ac.cn Wang, Wenlong; Zhao, Jimin; Bai, Xuedong E-mail: xdbai@iphy.ac.cn; Wang, Enge E-mail: xdbai@iphy.ac.cn

    2014-08-18

    The cathodoluminescence spectrum of single zinc oxide (ZnO) nanowires is measured by in-situ optical Transmission Electron Microscope. The coupling between exciton and longitudinal optical phonon is studied. The band edge emission varies for different excitation spots. This effect is attributed to the exciton propagation along the c axis of the nanowire. Contrary to free exciton emission, the phonon replicas are well confined in ZnO nanowire. They travel along the c axis and emit at the end surface. Bending strain increases the relative intensity of second order phonon replicas when excitons travel along the c-axis.

  2. Crystallographic analysis of the solid-state dewetting of polycrystalline gold film using automated indexing in a transmission electron microscope

    SciTech Connect (OSTI)

    Jang, S. A.; Lee, H. J.; Oh, Y. J.; Thompson, C. V.; Ross, C. A.

    2015-12-01

    We analyzed the effect of crystallographic anisotropy on the morphological evolution of a 12-nm-thick gold film during solid-state dewetting at high temperatures using automated indexing tool in a transmission electron microscopy. Dewetting initiated at grain-boundary triple junctions adjacent to large grains resulting from abnormal grain growth driven by (111) texture development. Voids at the junctions developed shapes with faceted edges bounded by low-index crystal planes. The kinetic mobility of the edges varied with the crystal orientation normal to the edges, with a predominance of specific edges with the slowest retraction rates as the annealing time was increased.

  3. Ultrafast electron transfer at organic semiconductor interfaces: Importance of molecular orientation

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Ayzner, Alexander L.; Nordlund, Dennis; Kim, Do -Hwan; Bao, Zhenan; Toney, Michael F.

    2014-12-04

    Much is known about the rate of photoexcited charge generation in at organic donor/acceptor (D/A) heterojunctions overaged over all relative arrangements. However, there has been very little experimental work investigating how the photoexcited electron transfer (ET) rate depends on the precise relative molecular orientation between D and A in thin solid films. This is the question that we address in this work. We find that the ET rate depends strongly on the relative molecular arrangement: The interface where the model donor compound copper phthalocyanine is oriented face-on with respect to the fullerene C60 acceptor yields a rate that is approximatelymore » 4 times faster than that of the edge-on oriented interface. Our results suggest that the D/A electronic coupling is significantly enhanced in the face-on case, which agrees well with theoretical predictions, underscoring the importance of controlling the relative interfacial molecular orientation.« less

  4. Ultrafast electron transfer at organic semiconductor interfaces: Importance of molecular orientation

    SciTech Connect (OSTI)

    Ayzner, Alexander L.; Nordlund, Dennis; Kim, Do -Hwan; Bao, Zhenan; Toney, Michael F.

    2014-12-04

    Much is known about the rate of photoexcited charge generation in at organic donor/acceptor (D/A) heterojunctions overaged over all relative arrangements. However, there has been very little experimental work investigating how the photoexcited electron transfer (ET) rate depends on the precise relative molecular orientation between D and A in thin solid films. This is the question that we address in this work. We find that the ET rate depends strongly on the relative molecular arrangement: The interface where the model donor compound copper phthalocyanine is oriented face-on with respect to the fullerene C60 acceptor yields a rate that is approximately 4 times faster than that of the edge-on oriented interface. Our results suggest that the D/A electronic coupling is significantly enhanced in the face-on case, which agrees well with theoretical predictions, underscoring the importance of controlling the relative interfacial molecular orientation.

  5. Fragment transition density method to calculate electronic coupling for excitation energy transfer

    SciTech Connect (OSTI)

    Voityuk, Alexander A.

    2014-06-28

    A general approach, the Fragment Transition Density (FTD) scheme, is introduced to estimate electronic coupling for excitation energy transfer in a molecular system. Within this method, the excitation energies and transition densities of the system are used to derive the coupling matrix element. The scheme allows one to treat systems where exciton donor and acceptor are close together and their exchange interaction and orbital overlap are significant. The FTD method can be applied in combination with any quantum mechanical approach to treat excited states of general nature including single-, double-, and higher excitations. Using FTD approach, we derive excitonic couplings for several systems computed with the CIS, TD DFT and MS-CASPT2 methods. In particular, it is shown that the estimated coupling values in DNA ?-stacks are strongly affected by the short-range electronic interaction of adjacent nucleobases.

  6. Coupled electron-nuclear dynamics: Charge migration and charge transfer initiated near a conical intersection

    SciTech Connect (OSTI)

    Mendive-Tapia, David; Vacher, Morgane; Bearpark, Michael J.; Robb, Michael A.

    2013-07-28

    Coupled electron-nuclear dynamics, implemented using the Ehrenfest method, has been used to study charge migration with fixed nuclei, together with charge transfer when nuclei are allowed to move. Simulations were initiated at reference geometries of neutral benzene and 2-phenylethylamine (PEA), and at geometries close to potential energy surface crossings in the cations. Cationic eigenstates, and the so-called sudden approximation, involving removal of an electron from a correlated ground-state wavefunction for the neutral species, were used as initial conditions. Charge migration without coupled nuclear motion could be observed if the Ehrenfest simulation, using the sudden approximation, was started near a conical intersection where the states were both strongly coupled and quasi-degenerate. Further, the main features associated with charge migration were still recognizable when the nuclear motion was allowed to couple. In the benzene radical cation, starting from the reference neutral geometry with the sudden approximation, one could observe sub-femtosecond charge migration with a small amplitude, which results from weak interaction with higher electronic states. However, we were able to engineer large amplitude charge migration, with a period between 10 and 100 fs, corresponding to oscillation of the electronic structure between the quinoid and anti-quinoid cationic electronic configurations, by distorting the geometry along the derivative coupling vector from the D{sub 6h} Jahn-Teller crossing to lower symmetry where the states are not degenerate. When the nuclear motion becomes coupled, the period changes only slightly. In PEA, in an Ehrenfest trajectory starting from the D{sub 2} eigenstate and reference geometry, a partial charge transfer occurs after about 12 fs near the first crossing between D{sub 1}, D{sub 2} (N{sup +}-Phenyl, N-Phenyl{sup +}). If the Ehrenfest propagation is started near this point, using the sudden approximation without coupled

  7. Mechanisms for Electron Transfer Through Pili to Fe(III) Oxide in Geobacter

    SciTech Connect (OSTI)

    Lovley, Derek R.

    2015-03-09

    The purpose of these studies was to aid the Department of Energy in its goal of understanding how microorganisms involved in the bioremediation of metals and radionuclides sustain their activity in the subsurface. This information is required in order to incorporate biological processes into decision making for environmental remediation and long-term stewardship of contaminated sites. The proposed research was designed to elucidate the mechanisms for electron transfer to Fe(III) oxides in Geobacter species because Geobacter species are abundant dissimilatory metal-reducing microorganisms in a diversity of sites in which uranium is undergoing natural attenuation via the reduction of soluble U(VI) to insoluble U(IV) or when this process is artificially stimulated with the addition of organic electron donors. This study investigated the novel, but highly controversial, concept that the final conduit for electron transfer to Fe(III) oxides are electrically conductive pili. The specific objectives were to: 1) further evaluate the conductivity along the pili of Geobacter sulfurreducens and related organisms; 2) determine the mechanisms for pili conductivity; and 3) investigate the role of pili in Fe(III) oxide reduction. The studies demonstrated that the pili of G. sulfurreducens are conductive along their length. Surprisingly, the pili possess a metallic-like conductivity similar to that observed in synthetic organic conducting polymers such as polyaniline. Detailed physical analysis of the pili, as well as studies in which the structure of the pili was genetically modified, demonstrated that the metallic-like conductivity of the pili could be attributed to overlapping pi-pi orbitals of aromatic amino acids. Other potential mechanisms for conductivity, such as electron hopping between cytochromes associated with the pili were definitively ruled out. Pili were also found to be essential for Fe(III) oxide reduction in G. metallireducens. Ecological studies demonstrated

  8. Fundamental studies of energy-and hole/electron- transfer in hydroporphyrin architectures

    SciTech Connect (OSTI)

    Bocian, David F.

    2014-08-20

    The long-term objective of the Bocian/Holten/Lindsey research program is to design, synthesize, and characterize tetrapyrrole-based molecular architectures that absorb sunlight, funnel energy, and separate charge with high efficiency and in a manner compatible with current and future solar-energy conversion schemes. The synthetic tetrapyrroles include porphyrins and hydroporphyrins; the latter classes of molecules encompass analogues of the naturally occurring chlorophylls and bacteriochlorophylls (e.g., chlorins, bacteriochlorins, and their derivatives). The attainment of the goals of the research program requires the close interplay of molecular design and synthesis (Lindsey group), static and time-resolved optical spectroscopic measurements (Holten group), and electrochemical, electron paramagnetic resonance, and resonance Raman studies, as well as density functional theory calculations (Bocian Group). The proposed research encompasses four interrelated themes: (1) Determination of the rates of ground-state hole/electron transfer between (hydro)porphyrins in multipigment arrays as a function of array size, distance between components, linker type, site of linker connection, and frontier molecular orbital composition. (2) Examination of excited-state energy transfer among hydroporphyrins in multipigment arrrays, including both pairwise and non-adjacent transfer, with a chief aim to identify the relative contributions of through-space (Förster) and through-bond (Dexter) mechanisms of energy transfer, including the roles of site of linker connection and frontier molecular orbital composition. (3) Elucidation of the role of substituents in tuning the spectral and electronic properties of bacteriochlorins, with a primary aim of learning how to shift the long-wavelength absorption band deeper into the near-infrared region. (4) Continued development of the software package PhotochemCAD for spectral manipulations and calculations through the compilation of a database

  9. Kinetics of liquid-mediated crystallization of amorphous Ge from multi-frame dynamic transmission electron microscopy

    SciTech Connect (OSTI)

    Santala, M. K. Campbell, G. H.; Raoux, S.

    2015-12-21

    The kinetics of laser-induced, liquid-mediated crystallization of amorphous Ge thin films were studied using multi-frame dynamic transmission electron microscopy (DTEM), a nanosecond-scale photo-emission transmission electron microscopy technique. In these experiments, high temperature gradients are established in thin amorphous Ge films with a 12-ns laser pulse with a Gaussian spatial profile. The hottest region at the center of the laser spot crystallizes in ∼100 ns and becomes nano-crystalline. Over the next several hundred nanoseconds crystallization continues radially outward from the nano-crystalline region forming elongated grains, some many microns long. The growth rate during the formation of these radial grains is measured with time-resolved imaging experiments. Crystal growth rates exceed 10 m/s, which are consistent with crystallization mediated by a very thin, undercooled transient liquid layer, rather than a purely solid-state transformation mechanism. The kinetics of this growth mode have been studied in detail under steady-state conditions, but here we provide a detailed study of liquid-mediated growth in high temperature gradients. Unexpectedly, the propagation rate of the crystallization front was observed to remain constant during this growth mode even when passing through large local temperature gradients, in stark contrast to other similar studies that suggested the growth rate changed dramatically. The high throughput of multi-frame DTEM provides gives a more complete picture of the role of temperature and temperature gradient on laser crystallization than previous DTEM experiments.

  10. Kinetics of liquid-mediated crystallization of amorphous Ge from multi-frame dynamic transmission electron microscopy

    SciTech Connect (OSTI)

    Santala, M. K.; Raoux, S.; Campbell, G. H.

    2015-12-24

    The kinetics of laser-induced, liquid-mediated crystallization of amorphous Ge thin films were studied using multi-frame dynamic transmission electron microscopy (DTEM), a nanosecond-scale photo-emission transmission electron microscopy technique. In these experiments, high temperature gradients are established in thin amorphous Ge films with a 12-ns laser pulse with a Gaussian spatial profile. The hottest region at the center of the laser spot crystallizes in ~100 ns and becomes nano-crystalline. Over the next several hundred nanoseconds crystallization continues radially outward from the nano-crystalline region forming elongated grains, some many microns long. The growth rate during the formation of these radial grains is measured with time-resolved imaging experiments. Crystal growth rates exceed 10 m/s, which are consistent with crystallization mediated by a very thin, undercooled transient liquid layer, rather than a purely solid-state transformation mechanism. The kinetics of this growth mode have been studied in detail under steady-state conditions, but here we provide a detailed study of liquid-mediated growth in high temperature gradients. Unexpectedly, the propagation rate of the crystallization front was observed to remain constant during this growth mode even when passing through large local temperature gradients, in stark contrast to other similar studies that suggested the growth rate changed dramatically. As a result, the high throughput of multi-frame DTEM provides gives a more complete picture of the role of temperature and temperature gradient on laser crystallization than previous DTEM experiments.

  11. Magnetic properties and transmission electron microscopy studies of Ni nanoparticles encapsulated in carbon nanocages and carbon nanotubes

    SciTech Connect (OSTI)

    He Chunnian; Zhao Naiqin Shi Chunsheng; Li Jiajun; Li Haipeng

    2008-08-04

    Three types of carbon nanomaterials, including bamboo-shaped carbon nanotubes with Ni encapsulated and hollow and Ni catalytic particles filled carbon nanocages, have been prepared by methane catalytic decomposition at a relatively low temperature. Transmission electron microscopy observations showed that fascinating fullerene-like Ni-C (graphitic) core-shell nanostructures predominated. Detailed examination of high-resolution transmission electron microscopy showed that the walls of bamboo-shaped carbon nanotubes with quasi-cone catalytic particles encapsulated consisted of oblique graphene planes with respect to the tube axis. The Ni particles encapsulated in the carbon nanocages were larger than that encapsulated in carbon nanotubes, but the diameters of the cores of hollow carbon nanocages were less than that of Ni particles encapsulated in carbon nanotubes, suggesting that the sizes of catalyst particles played an important role during carbon nanomaterial growth. The magnetic properties of the carbon nanomaterials were measured, which showed relatively large coercive force (H{sub c} = 138.4 O{sub e}) and good ferromagnetism (M{sub r}/M{sub s} = 0.325)

  12. High-speed multi-frame dynamic transmission electron microscope image acquisition system with arbitrary timing

    DOE Patents [OSTI]

    Reed, Bryan W.; DeHope, William J.; Huete, Glenn; LaGrange, Thomas B.; Shuttlesworth, Richard M.

    2016-02-23

    An electron microscope is disclosed which has a laser-driven photocathode and an arbitrary waveform generator (AWG) laser system ("laser"). The laser produces a train of temporally-shaped laser pulses each being of a programmable pulse duration, and directs the laser pulses to the laser-driven photocathode to produce a train of electron pulses. An image sensor is used along with a deflector subsystem. The deflector subsystem is arranged downstream of the target but upstream of the image sensor, and has a plurality of plates. A control system having a digital sequencer controls the laser and a plurality of switching components, synchronized with the laser, to independently control excitation of each one of the deflector plates. This allows each electron pulse to be directed to a different portion of the image sensor, as well as to enable programmable pulse durations and programmable inter-pulse spacings.

  13. High-speed multiframe dynamic transmission electron microscope image acquisition system with arbitrary timing

    DOE Patents [OSTI]

    Reed, Bryan W.; DeHope, William J.; Huete, Glenn; LaGrange, Thomas B.; Shuttlesworth, Richard M.

    2015-10-20

    An electron microscope is disclosed which has a laser-driven photocathode and an arbitrary waveform generator (AWG) laser system ("laser"). The laser produces a train of temporally-shaped laser pulses of a predefined pulse duration and waveform, and directs the laser pulses to the laser-driven photocathode to produce a train of electron pulses. An image sensor is used along with a deflector subsystem. The deflector subsystem is arranged downstream of the target but upstream of the image sensor, and has two pairs of plates arranged perpendicular to one another. A control system controls the laser and a plurality of switching components synchronized with the laser, to independently control excitation of each one of the deflector plates. This allows each electron pulse to be directed to a different portion of the image sensor, as well as to be provided with an independently set duration and independently set inter-pulse spacings.

  14. High-Resolution Transmission Electron Microscopy Observation of Colloidal Nanocrystal Growth Mechanisms using Graphene Liquid Cells

    SciTech Connect (OSTI)

    Yuk, Jong Min; Park, Jungwon; Ercius, Peter; Kim, Kwanpyo; Hellebusch, Danny J.; Crommie, Michael F.; Lee, Jeong Yong; Zettl, A.; Alivisatos, A. Paul

    2011-12-12

    We introduce a new type of liquid cell for in-situ electron microscopy based upon entrapment of a liquid film between layers of graphene. We employ this cell to achieve high-resolution imaging of colloidal platinum nanocrystal growth. The ability to directly image and resolve critical steps at atomic resolution provides new insights into nanocrystal coalescence and reshaping during growth.

  15. Dynamic Processes in Biology, Chemistry, and Materials Science: Opportunities for UltraFast Transmission Electron Microscopy - Workshop Summary Report

    SciTech Connect (OSTI)

    Kabius, Bernd C.; Browning, Nigel D.; Thevuthasan, Suntharampillai; Diehl, Barbara L.; Stach, Eric A.

    2012-07-25

    mission. This workshop built on previous workshops and included three breakout sessions identifying scientific challenges in biology, biogeochemistry, catalysis, and materials science frontier areas of fundamental science that underpin energy and environmental science that would significantly benefit from ultrafast transmission electron microscopy (UTEM). In addition, the current status of time-resolved electron microscopy was examined, and the technologies that will enable future advances in spatio-temporal resolution were identified in a fourth breakout session.

  16. Electron line shape and transmission function of the KATRIN monitor spectrometer

    SciTech Connect (OSTI)

    Slezk, M. [Faculty of Mathematics and Physics, Charles University, Ke Karlovu 3, 12116 Prague, Czech Republic and Nuclear Physics Institute, Academy of Sciences of the Czech Republic, Hlavn 130, 25068 ?e (Czech Republic)

    2013-12-30

    Knowledge of the neutrino mass is of particular interest in modern neutrino physics. Besides the neutrinoless double beta decay and cosmological observation information about the neutrino mass is obtained from single beta decay by observing the shape of the electron spectrum near the endpoint. The KATRIN ? decay experiment aims to push the limit on the effective electron antineutrino mass down to 0.2 eV/c{sup 2}. To reach this sensitivity several systematic effects have to be under control. One of them is the fluctuations of the absolute energy scale, which therefore has to be continuously monitored at very high precision. This paper shortly describes KATRIN, the technique for continuous monitoring of the absolute energy scale and recent improvements in analysis of the monitoring data.

  17. REAL-TIME TRACER MONITORING OF RESERVOIR STIMULATION PROCEDURES VIA ELECTRONIC WIRELINE AND TELEMETRY DATA TRANSMISSION

    SciTech Connect (OSTI)

    George Scott III

    2003-08-01

    Ongoing Phase 2-3 work comprises the final development and field-testing of two complementary real-time reservoir technologies; a stimulation process and a tracer fracturing diagnostic system. Initial DE-FC26-99FT40129 project work included research, development, and testing of the patented gamma tracer fracturing diagnostic system. This process was field-proven to be technically useful in providing tracer measurement of fracture height while fracturing; however, technical licensing restrictions blocked Realtimezone from fully field-testing this real-time gamma diagnostic system, as originally planned. Said restrictions were encountered during Phase 2 field test work as result of licensing limitations and potential conflicts between service companies participating in project work, as related to their gamma tracer logging tool technology. Phase 3 work principally demonstrated field-testing of Realtimezone (RTZ) and NETL's Downhole-mixed Reservoir Stimulation process. Early on, the simplicity of and success of downhole-mixing was evident from well tests, which were made commercially productive. A downhole-mixed acid stimulation process was tested successfully and is currently commercially used in Canada. The fourth well test was aborted due to well bore conditions, and an alternate test project is scheduled April, 2004. Realtimezone continues to effectuate ongoing patent protection in the United States and foreign markets. In 2002, Realtimezone and the NETL licensed their United States patent to Halliburton Energy Services (HES). Additional licensing arrangements with other industry companies are anticipated in 2004-2005. Ongoing Phase 2 and Phase 3 field-testing continues to confirm applications of both real-time technologies. Technical data transfer to industry is ongoing via Internet tech-transfer and various industry presentations and publications including Society of Petroleum Engineers. These real-time enhanced stimulation procedures should significantly

  18. Combining nanocalorimetry and dynamic transmission electron microscopy for in situ characterization of materials processes under rapid heating and cooling

    SciTech Connect (OSTI)

    Grapes, Michael D.; LaGrange, Thomas; Reed, Bryan W.; Campbell, Geoffrey H.; Friedman, Lawrence H.; LaVan, David A.; Weihs, Timothy P.

    2014-08-15

    Nanocalorimetry is a chip-based thermal analysis technique capable of analyzing endothermic and exothermic reactions at very high heating and cooling rates. Here, we couple a nanocalorimeter with an extremely fast in situ microstructural characterization tool to identify the physical origin of rapid enthalpic signals. More specifically, we describe the development of a system to enable in situ nanocalorimetry experiments in the dynamic transmission electron microscope (DTEM), a time-resolved TEM capable of generating images and electron diffraction patterns with exposure times of 30 ns500 ns. The full experimental system consists of a modified nanocalorimeter sensor, a custom-built in situ nanocalorimetry holder, a data acquisition system, and the DTEM itself, and is capable of thermodynamic and microstructural characterization of reactions over a range of heating rates (10{sup 2} K/s10{sup 5} K/s) accessible by conventional (DC) nanocalorimetry. To establish its ability to capture synchronized calorimetric and microstructural data during rapid transformations, this work describes measurements on the melting of an aluminum thin film. We were able to identify the phase transformation in both the nanocalorimetry traces and in electron diffraction patterns taken by the DTEM. Potential applications for the newly developed system are described and future system improvements are discussed.

  19. Electronic-excitation energy transfer in heterogeneous dye solutions under laser excitation

    SciTech Connect (OSTI)

    Levshin, L.V.; Mukushev, B.T.; Saletskii, A.M.

    1995-10-01

    An experimental study has been made of electronic-excitation energy transfer (EEET) among dye molecules of different types for different exciting-fight wavelengths and temperatures. Upon selective laser excitation of the donor, the inhomogeneous broadening of molecular levels increases the probability of EEET from the donor to acceptor molecules. The efficiency of this process is directly proportional to the acceptor molecule concentration and is temperature dependent. The EEET is accompanied by the spectral migration of energy among donor molecules, which reduces the fluorescence quantum efficiency of the donor. Increasing the frequency of the exciting light decreases in the donor fluorescence quantum efficiency. An increase in the acceptor molecule concentration results in a decrease of the spectral migration of excitation in the donor molecule system. 5 refs., 5 figs.

  20. Electron Transfer between Cytochrome C and Cytochome C Peroxidase in Single Crystals

    SciTech Connect (OSTI)

    Kang, Seong A.; Marjavaara, Pieti J.; Crane, Brian R.

    2010-11-10

    Cytochrome c (Cc) and cytochrome c peroxidase (CcP) form an important redox pair for understanding interprotein electron transfer (ET). Measurements of ET rates from photoexcited CcP substituted with Zn porphyrin to either yeast Fe(III)Cc or horse Fe(III)Cc in crystals reveal that the molecular associations found in the respective crystal structures determine solution reactivity. Similar forward rates for yeast isozyme-1 Cc (yCc) and yCc homologue horse Cc (hCc), despite different orientations relative to CcP, suggest small-amplitude conformational gating of ET even in the crystalline state; faster back ET in the yCc compared to the hCc complex agrees with the relative coupling between redox sites predicted by the structures.

  1. Investigation of Electron Transfer-Based Photonic and Electro-Optic Materials and Devices

    SciTech Connect (OSTI)

    Bromenshenk, Jerry J; Abbott, Edwin H; Dickensheets, David; Donovan, Richard P; Hobbs, J D; Spangler, Lee; McGuirl, Michele A; Spangler, Charles; Rebane, Aleksander; Rosenburg, Edward; Schmidt, V H; Singel, David J

    2008-03-28

    Montana's state program began its sixth year in 2006. The project's research cluster focused on physical, chemical, and biological materials that exhibit unique electron-transfer properties. Our investigators have filed several patents and have also have established five spin-off businesses (3 MSU, 2 UM) and a research center (MT Tech). In addition, this project involved faculty and students at three campuses (MSU, UM, MT Tech) and has a number of under-represented students, including 10 women and 5 Native Americans. In 2006, there was an added emphasis on exporting seminars and speakers via the Internet from UM to Chief Dull Knife Community College, as well as work with the MT Department of Commerce to better educate our faculty regarding establishing small businesses, licensing and patent issues, and SBIR program opportunities.

  2. Charge Transfer Fluorescence and 34 nm Exciton Diffusion Length in Polymers with Electron Acceptor End Traps

    SciTech Connect (OSTI)

    Zaikowski, L.; Mauro, G.; Bird, M.; Karten, B.; Asaoka, S.; Wu, Q.; Cook, A. R.; Miller, J.

    2014-12-22

    Photoexcitation of conjugated poly-2,7-(9,9-dihexylfluorene) polyfluorenes with naphthylimide (NI) and anthraquinone (AQ) electron-acceptor end traps produces excitons that form charge transfer states at the end traps. Intramolecular singlet exciton transport to end traps was examined by steady state fluorescence for polyfluorenes of 17 to 127 repeat units in chloroform, dimethylformamide (DMF), tetrahydrofuran (THF), and p-xylene. End traps capture excitons and form charge transfer (CT) states at all polymer lengths and in all solvents. The CT nature of the end-trapped states is confirmed by their fluorescence spectra, solvent and trap group dependence and DFT descriptions. Quantum yields of CT fluorescence are as large as 46%. This strong CT emission is understood in terms of intensity borrowing. Energies of the CT states from onsets of the fluorescence spectra give the depths of the traps which vary with solvent polarity. For NI end traps the trap depths are 0.06 (p-xylene), 0.13 (THF) and 0.19 eV (CHCl3). For AQ, CT fluorescence could be observed only in p-xylene where the trap depth is 0.27 eV. Quantum yields, emission energies, charge transfer energies, solvent reorganization and vibrational energies were calculated. Fluorescence measurements on chains >100 repeat units indicate that end traps capture ~50% of the excitons, and that the exciton diffusion length LD =34 nm, which is much larger than diffusion lengths reported in polymer films or than previously known for diffusion along isolated chains. The efficiency of exciton capture depends on chain length, but not on trap depth, solvent polarity or which trap group is present.

  3. Charge transfer fluorescence and 34 nm exciton diffusion length in polymers with electron acceptor end traps

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Zaikowski, Lori; Mauro, Gina; Bird, Matthew; Karten, Brianne; Asaoka, Sadayuki; Wu, Qin; Cook, Andrew R.; Miller, John R.

    2014-12-22

    Photoexcitation of conjugated poly-2,7-(9,9-dihexylfluorene) polyfluorenes with naphthylimide (NI) and anthraquinone (AQ) electron-acceptor end traps produces excitons that form charge transfer states at the end traps. Intramolecular singlet exciton transport to end traps was examined by steady state fluorescence for polyfluorenes of 17 to 127 repeat units in chloroform, dimethylformamide (DMF), tetrahydrofuran (THF), and p-xylene. End traps capture excitons and form charge transfer (CT) states at all polymer lengths and in all solvents. The CT nature of the end-trapped states is confirmed by their fluorescence spectra, solvent and trap group dependence and DFT descriptions. Quantum yields of CT fluorescence are asmore » large as 46%. This strong CT emission is understood in terms of intensity borrowing. Energies of the CT states from onsets of the fluorescence spectra give the depths of the traps which vary with solvent polarity. For NI end traps the trap depths are 0.06 (p-xylene), 0.13 (THF) and 0.19 eV (CHCl3). For AQ, CT fluorescence could be observed only in p-xylene where the trap depth is 0.27 eV. Quantum yields, emission energies, charge transfer energies, solvent reorganization and vibrational energies were calculated. Fluorescence measurements on chains >100 repeat units indicate that end traps capture ~50% of the excitons, and that the exciton diffusion length LD =34 nm, which is much larger than diffusion lengths reported in polymer films or than previously known for diffusion along isolated chains. As a result, the efficiency of exciton capture depends on chain length, but not on trap depth, solvent polarity or which trap group is present.« less

  4. Room temperature, hybrid sodium-based flow batteries with multi-electron transfer redox reactions

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; Sprenkle, Vincent L.

    2015-06-11

    We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volumemore » of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multielectron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. Furthermore, the critical barriers to mature this new HNFBs have also been explored.« less

  5. Room Temperature, Hybrid Sodium-Based Flow Batteries with Multi-Electron Transfer Redox Reactions

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; Sprenkle, Vincent L.

    2015-06-11

    We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volumemoreof the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multielectron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. The critical barriers to mature this new HNFBs have also been explored.less

  6. Real-time observation of morphological transformations in II-VI semiconducting nanobelts via environmental transmission electron microscopy

    SciTech Connect (OSTI)

    Agarwal, Rahul; Zakharov, Dmitri N.; Krook, Nadia M.; Liu, Wenjing; Berger, Jacob; Stach, Eric A.; Agarwal, Ritesh

    2015-05-01

    It has been observed that wurtzite II–VI semiconducting nanobelts transform into single-crystal, periodically branched nanostructures upon heating. The mechanism of this novel transformation has been elucidated by heating II–VI nanobelts in an environmental transmission electron microscope (ETEM) in oxidizing, reducing and inert atmospheres while observing their structural changes with high spatial resolution. The interplay of surface reconstruction of high-energy surfaces of the wurtzite phase and environment-dependent anisotropic chemical etching of certain crystal surfaces in the branching mechanism of nanobelts has been observed. Understanding of structural and chemical transformations of materials via in situ microscopy techniques and their role in designing new nanostructured materials is discussed.

  7. High-resolution transmission electron microscopy study of carbon deposited on the NiO/MgO solid solution catalysts

    SciTech Connect (OSTI)

    Hu, Y.H.; Ruckenstein, E.

    1999-05-15

    The carbon deposition due to the CH{sub 4} decomposition at 790 C over NiO/MgO catalysts was investigated by high-resolution transmission electron microscopy. While no deposits could be detected over the catalysts with a NiO content smaller than 9.1 wt%, they were detected over the catalysts with NiO contents of 23 and 50 wt%. The carbon deposits are composed of platelets located at distances of about 0.34 nm, corresponding to the graphitic carbon. Various structures of the deposited carbon were observed: (a) carbon consisting of platelets parallel to the surface of the particle, which covers a catalyst particle, (b) nanotubes composed of platelets parallel to their axis, and (c) carbon vortexes consisting of platelets parallel to their axis.

  8. Hot-stage transmission electron microscopy study of (Na, K)NbO{sub 3} based lead-free piezoceramics

    SciTech Connect (OSTI)

    Lu, Shengbo; Xu, Zhengkui; Kwok, K. W.; Chan, Helen L. W.

    2014-07-28

    Hierarchical nanodomains assembled into micron-sized stripe domains, which is believed to be associated with outstanding piezoelectric properties, were observed at room temperature in a typical lead free piezoceramics, (Na{sub 0.52}K{sub 0.48−x})(Nb{sub 0.95−x}Ta{sub 0.05})-xLiSbO{sub 3}, with finely tuned polymorphic phase boundaries (x = 0.0465) by transmission electron microscopy. The evolution of domain morphology and crystal structure under heating and cooling cycles in the ceramic was investigated by in-situ hot stage study. It is found that the nanodomains are irreversibly transformed into micron-sized rectangular domains during heating and cooling cycles, which lead to the thermal instability of piezoelectric properties of the materials.

  9. Direct Visualization of Solid Electrolyte Interphase Formation in Lithium-Ion Batteries with In Situ Electrochemical Transmission Electron Microscopy

    SciTech Connect (OSTI)

    Unocic, Raymond R; Sun, Xiao-Guang; Sacci, Robert L; Adamczyk, Leslie A; Alsem, Daan Hein; Dai, Sheng; Dudney, Nancy J; More, Karren Leslie

    2014-01-01

    Complex, electrochemically driven transport processes form the basis of electrochemical energy storage devices. The direct imaging of electrochemical processes at high spatial resolution and within their native liquid electrolyte would significantly enhance our understanding of device functionality, but has remained elusive. In this work we use a recently developed liquid cell for in situ electrochemical transmission electron microscopy to obtain insight into the electrolyte decomposition mechanisms and kinetics in lithium-ion (Li-ion) batteries by characterizing the dynamics of solid electrolyte interphase (SEI) formation and evolution. Here we are able to visualize the detailed structure of the SEI that forms locally at the electrode/electrolyte interface during lithium intercalation into natural graphite from an organic Li-ion battery electrolyte. We quantify the SEI growth kinetics and observe the dynamic self-healing nature of the SEI with changes in cell potential.

  10. Real-time observation of morphological transformations in II-VI semiconducting nanobelts via environmental transmission electron microscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Agarwal, Rahul; Zakharov, Dmitri N.; Krook, Nadia M.; Liu, Wenjing; Berger, Jacob; Stach, Eric A.; Agarwal, Ritesh

    2015-05-01

    It has been observed that wurtzite II–VI semiconducting nanobelts transform into single-crystal, periodically branched nanostructures upon heating. The mechanism of this novel transformation has been elucidated by heating II–VI nanobelts in an environmental transmission electron microscope (ETEM) in oxidizing, reducing and inert atmospheres while observing their structural changes with high spatial resolution. The interplay of surface reconstruction of high-energy surfaces of the wurtzite phase and environment-dependent anisotropic chemical etching of certain crystal surfaces in the branching mechanism of nanobelts has been observed. Understanding of structural and chemical transformations of materials via in situ microscopy techniques and their role in designingmore » new nanostructured materials is discussed.« less

  11. In situ observation on hydrogenation of Mg-Ni films using environmental transmission electron microscope with aberration correction

    SciTech Connect (OSTI)

    Matsuda, Junko; Yoshida, Kenta; Sasaki, Yukichi; Uchiyama, Naoki; Akiba, Etsuo

    2014-08-25

    In situ transmission electron microscopy (TEM) was performed to observe the hydrogenation of Mg-Ni films in a hydrogen atmosphere of 80100?Pa. An aberration-corrected environmental TEM with a differential pumping system allows us to reveal the Angstrom-scale structure of the films in the initial stage of hydrogenation: first, nucleation and growth of Mg{sub 2}NiH{sub 4} crystals with a lattice spacing of 0.22?nm in an Mg-rich amorphous matrix of the film occurs within 20 s after the start of the high-resolution observation, then crystallization of MgH{sub 2} with a smaller spacing of 0.15?nm happens after approximately 1?min. Our in situ TEM method is also applicable to the analysis of other hydrogen-related materials.

  12. Optimal experimental design for the detection of light atoms from high-resolution scanning transmission electron microscopy images

    SciTech Connect (OSTI)

    Gonnissen, J.; De Backer, A.; Martinez, G. T.; Van Aert, S.; Dekker, A. J. den; Rosenauer, A.; Sijbers, J.

    2014-08-11

    We report an innovative method to explore the optimal experimental settings to detect light atoms from scanning transmission electron microscopy (STEM) images. Since light elements play a key role in many technologically important materials, such as lithium-battery devices or hydrogen storage applications, much effort has been made to optimize the STEM technique in order to detect light elements. Therefore, classical performance criteria, such as contrast or signal-to-noise ratio, are often discussed hereby aiming at improvements of the direct visual interpretability. However, when images are interpreted quantitatively, one needs an alternative criterion, which we derive based on statistical detection theory. Using realistic simulations of technologically important materials, we demonstrate the benefits of the proposed method and compare the results with existing approaches.

  13. Kinetics of liquid-mediated crystallization of amorphous Ge from multi-frame dynamic transmission electron microscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Santala, M. K.; Raoux, S.; Campbell, G. H.

    2015-12-24

    The kinetics of laser-induced, liquid-mediated crystallization of amorphous Ge thin films were studied using multi-frame dynamic transmission electron microscopy (DTEM), a nanosecond-scale photo-emission transmission electron microscopy technique. In these experiments, high temperature gradients are established in thin amorphous Ge films with a 12-ns laser pulse with a Gaussian spatial profile. The hottest region at the center of the laser spot crystallizes in ~100 ns and becomes nano-crystalline. Over the next several hundred nanoseconds crystallization continues radially outward from the nano-crystalline region forming elongated grains, some many microns long. The growth rate during the formation of these radial grains is measuredmore » with time-resolved imaging experiments. Crystal growth rates exceed 10 m/s, which are consistent with crystallization mediated by a very thin, undercooled transient liquid layer, rather than a purely solid-state transformation mechanism. The kinetics of this growth mode have been studied in detail under steady-state conditions, but here we provide a detailed study of liquid-mediated growth in high temperature gradients. Unexpectedly, the propagation rate of the crystallization front was observed to remain constant during this growth mode even when passing through large local temperature gradients, in stark contrast to other similar studies that suggested the growth rate changed dramatically. As a result, the high throughput of multi-frame DTEM provides gives a more complete picture of the role of temperature and temperature gradient on laser crystallization than previous DTEM experiments.« less

  14. Excitonic splitting and coherent electronic energy transfer in the gas-phase benzoic acid dimer

    SciTech Connect (OSTI)

    Ottiger, Philipp; Leutwyler, Samuel

    2012-11-28

    The benzoic acid dimer, (BZA){sub 2}, is a paradigmatic symmetric hydrogen bonded dimer with two strong antiparallel hydrogen bonds. The excitonic S{sub 1}/S{sub 2} state splitting and coherent electronic energy transfer within supersonically cooled (BZA){sub 2} and its {sup 13}C-, d{sub 1}-, d{sub 2}-, and {sup 13}C/d{sub 1}- isotopomers have been investigated by mass-resolved two-color resonant two-photon ionization spectroscopy. The (BZA){sub 2}-(h-h) and (BZA){sub 2}-(d-d) dimers are C{sub 2h} symmetric, hence only the S{sub 2} Leftwards-Arrow S{sub 0} transition can be observed, the S{sub 1} Leftwards-Arrow S{sub 0} transition being strictly electric-dipole forbidden. A single {sup 12}C/{sup 13}C or H/D isotopic substitution reduces the symmetry of the dimer to C{sub s}, so that the isotopic heterodimers (BZA){sub 2}-{sup 13}C, (BZA){sub 2}-(h-d), (BZA){sub 2}-(h{sup 13}C-d), and (BZA){sub 2}-(h-d{sup 13}C) show both S{sub 1} Leftwards-Arrow S{sub 0} and S{sub 2} Leftwards-Arrow S{sub 0} bands. The S{sub 1}/S{sub 2} exciton splitting inferred is {Delta}{sub exc}= 0.94 {+-} 0.1 cm{sup -1}. This is the smallest splitting observed so far for any H-bonded gas-phase dimer. Additional isotope-dependent contributions to the splittings, {Delta}{sub iso}, arise from the change of the zero-point vibrational energy upon electronic excitation and range from {Delta}{sub iso}= 3.3 cm{sup -1} upon {sup 12}C/{sup 13}C substitution to 14.8 cm{sup -1} for carboxy H/D substitution. The degree of excitonic localization/delocalization can be sensitively measured via the relative intensities of the S{sub 1} Leftwards-Arrow S{sub 0} and S{sub 2} Leftwards-Arrow S{sub 0} origin bands; near-complete localization is observed even for a single {sup 12}C/{sup 13}C substitution. The S{sub 1}/ S{sub 2} energy gap of (BZA){sub 2} is {Delta}{sub calc}{sup exc}=11 cm{sup -1} when calculated by the approximate second-order perturbation theory (CC2) method. Upon correction for vibronic

  15. Redox linked flavin sites in extracellular decaheme proteins involved in microbe-mineral electron transfer.

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Edwards, Marcus J.; White, Gaye F.; Norman, Michael; Tome-Fernandez, Alice; Ainsworth, Emma; Shi, Liang; Fredrickson, Jim K.; Zachara, John M.; Butt, Julea N.; Richardson, David J.; et al

    2015-07-01

    Extracellular microbe-mineral electron transfer is a major driving force for the oxidation of organic carbon in many subsurface environments. Extracellular multi-heme cytochromes of the Shewenella genus play a major role in this process but the mechanism of electron exchange at the interface between cytochrome and acceptor is widely debated. The 1.8 Å x-ray crystal structure of the decaheme MtrC revealed a highly conserved CX₈C disulfide that, when substituted for AX₈A, severely compromised the ability of S. oneidensis to grow under aerobic conditions. Reductive cleavage of the disulfide in the presence of flavin mononucleotide (FMN) resulted in the reversible formation ofmore » a stable flavocytochrome. Similar results were also observed with other decaheme cytochromes, OmcA, MtrF and UndA. The data suggest that these decaheme cytochromes can transition between highly reactive flavocytochromes or less reactive cytochromes, and that this transition is controlled by a redox active disulfide that responds to the presence of oxygen.« less

  16. Redox linked flavin sites in extracellular decaheme proteins involved in microbe-mineral electron transfer.

    SciTech Connect (OSTI)

    Edwards, Marcus J.; White, Gaye F.; Norman, Michael; Tome-Fernandez, Alice; Ainsworth, Emma; Shi, Liang; Fredrickson, Jim K.; Zachara, John M.; Butt, Julea N.; Richardson, David J.; Clarke, Thomas A.

    2015-07-01

    Extracellular microbe-mineral electron transfer is a major driving force for the oxidation of organic carbon in many subsurface environments. Extracellular multi-heme cytochromes of the Shewenella genus play a major role in this process but the mechanism of electron exchange at the interface between cytochrome and acceptor is widely debated. The 1.8 Å x-ray crystal structure of the decaheme MtrC revealed a highly conserved CX₈C disulfide that, when substituted for AX₈A, severely compromised the ability of S. oneidensis to grow under aerobic conditions. Reductive cleavage of the disulfide in the presence of flavin mononucleotide (FMN) resulted in the reversible formation of a stable flavocytochrome. Similar results were also observed with other decaheme cytochromes, OmcA, MtrF and UndA. The data suggest that these decaheme cytochromes can transition between highly reactive flavocytochromes or less reactive cytochromes, and that this transition is controlled by a redox active disulfide that responds to the presence of oxygen.

  17. Thermodynamic Prediction of Compositional Phases Confirmed by Transmission Electron Microscopy on Tantalum-Based Alloy Weldments

    SciTech Connect (OSTI)

    Moddeman, William E.; Birkbeck, Janine C.; Barklay, Chadwick D.; Kramer, Daniel P.; Miller, Roger G.; Allard, Lawrence F.

    2007-01-30

    Tantalum alloys have been used by the U.S. Department of Energy as structural alloys for radioisotope based thermal to electrical power systems since the 1960s. Tantalum alloys are attractive for high temperature structural applications due to their high melting point, excellent formability, good thermal conductivity, good ductility (even at low temperatures), corrosion resistance, and weldability. Tantalum alloys have demonstrated sufficient high-temperature toughness to survive prolonged exposure to the radioisotope power-system working environment. Typically, the fabrication of power systems requires the welding of various components including the structural members made of tantalum alloys. Issues such as thermodynamics, lattice structure, weld pool dynamics, material purity and contamination, and welding atmosphere purity all potentially confound the understanding of the differences between the weldment properties of the different tantalum-based alloys. The objective of this paper is to outline the thermodynamically favorable material phases in tantalum alloys, with and without small amounts of hafnium, during and following solidification, based on the results derived from the FactSage(c) Integrated Thermodynamic Databank. In addition, Transition Electron Microscopy (TEM) data will show for the first time, the changes occurring in the HfC before and after welding, and the data will elucidate the role HfC plays in pinning grain boundaries.

  18. Probing the Degradation Mechanisms in Electrolyte Solutions for Li-ion Batteries by In-Situ Transmission Electron Microscopy

    SciTech Connect (OSTI)

    Abellan Baeza, Patricia; Mehdi, Beata L.; Parent, Lucas R.; Gu, Meng; Park, Chiwoo; Xu, Wu; Zhang, Yaohui; Arslan, Ilke; Zhang, Jiguang; Wang, Chong M.; Evans, James E.; Browning, Nigel D.

    2014-02-21

    One of the goals in the development of new battery technologies is to find new electrolytes with increased electrochemical stability. In-situ (scanning) transmission electron microscopy ((S)TEM) using an electrochemical fluid cell provides the ability to rapidly and directly characterize electrode/electrolyte interfacial reactions under battery relevant electrochemical conditions. Furthermore, as the electron beam itself causes a localized electrochemical reaction when it interacts with the electrolyte, the breakdown products that occur during the first stages of battery operation can potentially be simulated and characterized using a straightforward in-situ liquid stage (without electrochemical biasing capabilities). In this paper, we have studied the breakdown of a range of inorganic/salt complexes that are used in state-of-the-art Li-ion battery systems. The results of the in-situ (S)TEM experiments matches with previous stability tests performed during battery operation and the breakdown products and mechanisms are also consistent with known mechanisms. This analysis indicates that in-situ liquid stage (S)TEM observations can be used to directly test new electrolyte designs and provide structural insights into the origin of the solid electrolyte interphase (SEI) formation mechanism.

  19. Phase Boundary Propagation in Li-Alloying Battery Electrodes Revealed by Liquid-Cell Transmission Electron Microscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Leenheer, Andrew J.; Jungjohann, Katherine L.; Zavadil, Kevin R.; Harris, Charles T.

    2016-05-31

    Battery cycle life is directly influenced by the microstructural changes occurring in the electrodes during charge and discharge cycles. In this study, we image in situ the nanoscale phase evolution in negative electrode materials for Li-ion batteries using a fully enclosed liquid cell in a transmission electron microscope (TEM) to reveal early degradation that is not evident in the charge–discharge curves. To compare the electrochemical phase transformation behavior between three model materials, thin films of amorphous Si, crystalline Al, and crystalline Au were lithiated and delithiated at controlled rates while immersed in a commercial liquid electrolyte. This method allowed formore » the direct observation of lithiation mechanisms in nanoscale negative electrodes, revealing that a simplistic model of a surface-to-interior lithiation front is insufficient. For the crystalline films, a lithiation front spread laterally from a few initial nucleation points, with continued grain nucleation along the growing interface. The intermediate lithiated phases were identified using electron diffraction, and high-resolution postmortem imaging revealed the details of the final microstructure. Lastly, our results show that electrochemically induced solid–solid phase transformations can lead to highly concentrated stresses at the laterally propagating phase boundary which should be considered for future designs of nanostructured electrodes for Li-ion batteries.« less

  20. Lithium electrodeposition dynamics in aprotic electrolyte observed in situ via transmission electron microscopy

    SciTech Connect (OSTI)

    Leenheer, Andrew Jay; Jungjohann, Katherine Leigh; Zavadil, Kevin Robert; Sullivan, John P.; Harris, Charles Thomas

    2015-03-18

    Electrodeposited metallic lithium is an ideal negative battery electrode, but nonuniform microstructure evolution during cycling leads to degradation and safety issues. A better understanding of the Li plating and stripping processes is needed to enable practical Li-metal batteries. Here we use a custom microfabricated, sealed liquid cell for in situ scanning transmission electron microscopy (STEM) to image the first few cycles of lithium electrodeposition/dissolution in liquid aprotic electrolyte at submicron resolution. Cycling at current densities from 1 to 25 mA/cm2 leads to variations in grain structure, with higher current densities giving a more needle-like, higher surface area deposit. The effect of the electron beam was explored, and it was found that, even with minimal beam exposure, beam-induced surface film formation could alter the Li microstructure. The electrochemical dissolution was seen to initiate from isolated points on grains rather than uniformly across the Li surface, due to the stabilizing solid electrolyte interphase surface film. As a result, we discuss the implications for operando STEM liquid-cell imaging and Li-battery applications.

  1. In-situ Study of Dynamic Phenomena at Metal Nanosolder Interfaces Using Aberration Corrected Scanning Transmission Electron Microcopy.

    SciTech Connect (OSTI)

    Lu, Ping

    2014-10-01

    Controlling metallic nanoparticle (NP) interactions plays a vital role in the development of new joining techniques (nanosolder) that bond at lower processing temperatures but remain viable at higher temperatures. The pr imary objective of this project is t o develop a fundamental understanding of the actual reaction processes, associated atomic mechanisms, and the resulting microstructure that occur during thermally - driven bond formation concerning metal - metal nano - scale (<50nm) interfaces. In this LDRD pr oject, we have studied metallic NPs interaction at the elevated temperatures by combining in - situ transmission electron microscopy (TEM ) using an aberration - corrected scanning transmission electron microscope (AC - STEM) and atomic - scale modeling such as m olecular dynamic (MD) simulations. Various metallic NPs such as Ag, Cu and Au are synthesized by chemical routines. Numerous in - situ e xperiments were carried out with focus of the research on study of Ag - Cu system. For the first time, using in - situ STEM he ating experiments , we directly observed t he formation of a 3 - dimensional (3 - D) epitaxial Cu - Ag core - shell nanoparticle during the thermal interaction of Cu and Ag NPs at elevated temperatures (150 - 300 o C). The reaction takes place at temperatures as low as 150 o C and was only observed when care was taken to circumvent the effects of electron beam irradiation during STEM imaging. Atomic - scale modeling verified that the Cu - Ag core - shell structure is energetically favored, and indicated that this phenomenon is a nano - scale effect related to the large surface - to - volume ratio of the NPs. The observation potentially can be used for developing new nanosolder technology that uses Ag shell as the %22glue%22 that stic ks the particles of Cu together. The LDRD has led to several journal publications and numerous conference presentations, and a TA. In addition, we have developed new TEM characterization techniques and phase

  2. Directly correlated transmission electron microscopy and atom probe tomography of grain boundary oxidation in a Ni-Al binary alloy exposed to high-temperature water.

    SciTech Connect (OSTI)

    Schreiber, Daniel K.; Olszta, Matthew J.; Bruemmer, Stephen M.

    2013-10-30

    Intergranular oxidation of a Ni-4Al alloy exposed to hydrogenated, high-temperature water was characterized using directly correlated transmission electron microscopy and atom probe tomography. These combined analyses revealed that discrete, well-separated oxides (NiAl2O4) precipitated along grain boundaries in the metal. Aluminum was depleted from the grain boundary between oxides and also from one side of the boundary as a result of grain boundary migration. The discrete oxide morphology, disconnected from the continuous surface oxidation, suggests intergranular solid-state internal oxidation of Al. Keywords: oxidation; grain boundaries; nickel alloys; atom probe tomography; transmission electron microscopy (TEM)

  3. Transparent Conductors from Carbon Nanotubes LBL-Assembled with Polymer Dopant with ?-? Electron Transfer

    SciTech Connect (OSTI)

    Zhu, Jian; Shim, Bong Sup; Di Prima, Matthew; Kotov, Nicholas A.

    2011-01-01

    Single-walled carbon nanotube (SWNT) and other carbon-based coatings are being considered as replacements for indium tin oxide (ITO). The problems of transparent conductors (TCs) coatings from SWNT and similar materials include poor mechanical properties, high roughness, low temperature resilience, and fast loss of conductivity. The simultaneous realization of these desirable characteristics can be achieved using high structural control of layer-by-layer (LBL) deposition, which is demonstrated by the assembly of hydroethyl cellulose (HOCS) and sulfonated polyetheretherketone (SPEEK)-SWNTs. A new type of SWNT doping based on electron transfer from valence bands of nanotubes to unoccupied levels of SPEEK through ?-? interactions was identified for this system. It leads to a conductivity of 1.1 10? S/m at 66 wt % loadings of SWNT. This is better than other polymer/SWNT composites and translates into surface conductivity of 920 ?/? and transmittance of 86.7% at 550 nm. The prepared LBL films also revealed unusually high temperature resilience up to 500 C, and low roughness of 3.5 nm (ITO glass -2.4 nm). Tensile modulus, ultimate strength, and toughness of such coatings are 13 2 GPa, 366 35 MPa, and 8 3 kJ/m, respectively, and exceed corresponding parameters of all similar TCs. The cumulative figure of merit, ?TC, which included the critical failure strain relevant for flexible electronics, was ?TC = 0.022 and should be compared to ?TC = 0.006 for commercial ITO. Further optimization is possible using stratified nanoscale coatings and improved doping from the macromolecular LBL components.

  4. Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Canton, Sophie E.; Kjær, Kasper S.; Vankó, György; van Driel, Tim B.; Adachi, Shin -ichi; Bordage, Amélie; Bressler, Christian; Chabera, Pavel; Christensen, Morten; Dohn, Asmus O.; et al

    2015-03-02

    Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances.more » Thus experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined.« less

  5. Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

    SciTech Connect (OSTI)

    Canton, Sophie E.; Kjr, Kasper S.; Vank, Gyrgy; van Driel, Tim B.; Adachi, Shin -ichi; Bordage, Amlie; Bressler, Christian; Chabera, Pavel; Christensen, Morten; Dohn, Asmus O.; Galler, Andreas; Gawelda, Wojciech; Gosztola, David; Haldrup, Kristoffer; Harlang, Tobias; Liu, Yizhu; Mller, Klaus B.; Nmeth, Zoltn; Nozawa, Shunsuke; Ppai, Mtys; Sato, Tokushi; Sato, Takahiro; Suarez-Alcantara, Karina; Togashi, Tadashi; Tono, Kensuke; Uhlig, Jens; Vithanage, Dimali A.; Wrnmark, Kenneth; Yabashi, Makina; Zhang, Jianxin; Sundstrm, Villy; Nielsen, Martin M.

    2015-03-02

    Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donoracceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances. Thus experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined.

  6. Size and Temperature Dependence of Electron Transfer between CdSe Quantum Dots and a TiO 2 Nanobelt

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Tafen, De Nyago; Prezhdo, Oleg V.

    2015-02-24

    Understanding charge transfer reactions between quantum dots (QD) and metal oxides is fundamental for improving photocatalytic, photovoltaic and electronic devices. The complexity of these processes makes it difficult to find an optimum QD size with rapid charge injection and low recombination. We combine time-domain density functional theory with nonadiabatic molecular dynamics to investigate the size and temperature dependence of the experimentally studied electron transfer and charge recombination at CdSe QD-TiO2 nanobelt (NB) interfaces. The electron injection rate shows strong dependence on the QD size, increasing for small QDs. The rate exhibits Arrhenius temperature dependence, with the activation energy of themore » order of millielectronvolts. The charge recombination process occurs due to coupling of the electronic subsystem to vibrational modes of the TiO2 NB. Inelastic electron-phonon scattering happens on a picosecond time scale, with strong dependence on the QD size. Our simulations demonstrate that the electron-hole recombination rate decreases significantly as the QD size increases, in excellent agreement with experiments. The temperature dependence of the charge recombination rates can be successfully modeled within the framework of the Marcus theory through optimization of the electronic coupling and the reorganization energy. Our simulations indicate that by varying the QD size, one can modulate the photoinduced charge separation and charge recombination, fundamental aspects of the design principles for high efficiency devices.« less

  7. Transmission electron microscopy study of precipitates in an artificially aged Al–12.7Si–0.7Mg alloy

    SciTech Connect (OSTI)

    Liu, Fang; Yu, Fuxiao; Zhao, Dazhi; Zuo, Liang

    2015-09-15

    An investigation of Al–12.7Si–0.7Mg alloy aged at 160 °C, 180 °C and 200 °C for 3 h was carried out in order to identify the precipitating phases. Regular transmission and high resolution electron microscopy (TEM and HREM) were employed for this purpose. The studies were focused on the dark spots and needle-shaped precipitates lying in (001){sub Al} plane. Based on the HREM observations, dark spots and needle-shaped precipitates have different characteristics. The results revealed that the ellipsoidal and needle-shaped precipitates along <100> direction of the matrix coexist in the alloy by tilting experiments at given aging condition. The ellipsoidal dark spot precipitates viewing along [001]{sub Al} is not cross-sectional image of needle-shaped precipitates along <001>{sub Al}. Needle-shaped precipitate is coherent with the matrix. The diffraction pattern associated with the ellipsoidal precipitates is consistent with β″ reported in literature. - Highlights: • Wrought Al–Si–Mg alloy has been investigated to identify the precipitating phases. • The ellipsoidal and needle-shaped precipitates coexist in wrought Al–Si–Mg alloy. • The needle-shaped and ellipsoidal precipitates exhibit different characteristics.

  8. High speed direct imaging of thin metal film ablation by movie-mode dynamic transmission electron microscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Hihath, Sahar; Santala, Melissa K.; Cen, Xi; Campbell, Geoffrey; van Benthem, Klaus

    2016-03-11

    Obliteration of matter by pulsed laser beams is not only prevalent in science fiction movies, but finds numerous technological applications ranging from additive manufacturing over machining of micro- and nanostructured features to health care. Pulse lengths ranging from femtoseconds to nanoseconds are utilized at varying laser beam energies and pulse lengths, and enable the removal of nanometric volumes of material. While the mechanisms for removal of material by laser irradiation, i.e., laser ablation, are well understood on the micrometer length scale, it was previously impossible to directly observe obliteration processes on smaller scales due to experimental limitations for the combinationmore » of nanometer spatial and nanosecond temporal resolution. Here, we report the direct observation of metal thin film ablation from a solid substrate through dynamic transmission electron microscopy. Quantitative analysis reveals liquid-phase dewetting of the thin-film, followed by hydrodynamic sputtering of nano- to submicron sized metal droplets. We discovered unexpected fracturing of the substrate due to evolving thermal stresses. This study confirms that hydrodynamic sputtering remains a valid mechanism for droplet expulsion on the nanoscale, while irradiation induced stress fields represent limit laser processing of nanostructured materials. Ultimately, our results allow for improved safety during laser ablation in manufacturing and medical applications.« less

  9. Separating strain from composition in unit cell parameter maps obtained from aberration corrected high resolution transmission electron microscopy imaging

    SciTech Connect (OSTI)

    Schulz, T.; Remmele, T.; Korytov, M.; Markurt, T.; Albrecht, M.; Duff, A.; Lymperakis, L.; Neugebauer, J.; Chèze, C.

    2014-01-21

    Based on the evaluation of lattice parameter maps in aberration corrected high resolution transmission electron microscopy images, we propose a simple method that allows quantifying the composition and disorder of a semiconductor alloy at the unit cell scale with high accuracy. This is realized by considering, next to the out-of-plane, also the in-plane lattice parameter component allowing to separate the chemical composition from the strain field. Considering only the out-of-plane lattice parameter component not only yields large deviations from the true local alloy content but also carries the risk of identifying false ordering phenomena like formations of chains or platelets. Our method is demonstrated on image simulations of relaxed supercells, as well as on experimental images of an In{sub 0.20}Ga{sub 0.80}N quantum well. Principally, our approach is applicable to all epitaxially strained compounds in the form of quantum wells, free standing islands, quantum dots, or wires.

  10. Real time nanoscale structural evaluation of gold structures on Si (100) surface using in-situ transmission electron microscopy

    SciTech Connect (OSTI)

    Rath, A. E-mail: ashutosh.phy@gmail.com E-mail: pvsatyam22@gmail.com; Juluri, R. R.; Satyam, P. V. E-mail: ashutosh.phy@gmail.com E-mail: pvsatyam22@gmail.com

    2014-05-14

    Transport behavior of gold nanostructures on Si(100) substrate during annealing under high vacuum has been investigated using in-situ real time transmission electron microscopy (TEM). A comparative study has been done on the morphological changes due to annealing under different vacuum environments. Au thin films of thickness ∼2.0 nm were deposited on native oxide covered silicon substrate by using thermal evaporation system. In-situ real time TEM measurements at 850 °C showed the isotropic growth of rectangular/square shaped gold-silicon alloy structures. During the growth, it is observed that the alloying occurs in liquid phase followed by transformation into the rectangular shapes. For similar system, ex-situ annealing in low vacuum (10{sup −2} millibars) at 850 °C showed the spherical gold nanostructures with no Au-Si alloy formation. Under low vacuum annealing conditions, the rate of formation of the oxide layer dominates the oxide desorption rate, resulting in the creation of a barrier layer between Au and Si, which restricts the inter diffusion of Au in to Si. This work demonstrates the important role of interfacial oxide layer on the growth of nanoscale Au-Si alloy structures during the initial growth. The time dependent TEM images are presented to offer a direct insight into the fundamental dynamics of the sintering process at the nanoscale.

  11. Interaction potentials of anisotropic nanocrystals from the trajectory sampling of particle motion using in situ liquid phase transmission electron microscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Chen, Qian; Cho, Hoduk; Manthiram, Karthish; Yoshida, Mark; Ye, Xingchen; Alivisatos, A. Paul

    2015-03-23

    We demonstrate a generalizable strategy to use the relative trajectories of pairs and groups of nanocrystals, and potentially other nanoscale objects, moving in solution which can now be obtained by in situ liquid phase transmission electron microscopy (TEM) to determine the interaction potentials between nanocrystals. Such nanoscale interactions are crucial for collective behaviors and applications of synthetic nanocrystals and natural biomolecules, but have been very challenging to measure in situ at nanometer or sub-nanometer resolution. Here we use liquid phase TEM to extract the mathematical form of interaction potential between nanocrystals from their sampled trajectories. We show the power ofmore » this approach to reveal unanticipated features of nanocrystal–nanocrystal interactions by examining the anisotropic interaction potential between charged rod-shaped Au nanocrystals (Au nanorods); these Au nanorods assemble, in a tip-to-tip fashion in the liquid phase, in contrast to the well-known side-by-side arrangements commonly observed for drying-mediated assembly. These observations can be explained by a long-range and highly anisotropic electrostatic repulsion that leads to the tip-selective attachment. As a result, Au nanorods stay unassembled at a lower ionic strength, as the electrostatic repulsion is even longer-ranged. Our study not only provides a mechanistic understanding of the process by which metallic nanocrystals assemble but also demonstrates a method that can potentially quantify and elucidate a broad range of nanoscale interactions relevant to nanotechnology and biophysics.« less

  12. Correlative transmission electron microscopy and electrical properties study of switchable phase-change random access memory line cells

    SciTech Connect (OSTI)

    Oosthoek, J. L. M.; Kooi, B. J.; Voogt, F. C.; Attenborough, K.; Verheijen, M. A.; Hurkx, G. A. M.; Gravesteijn, D. J.

    2015-02-14

    Phase-change memory line cells, where the active material has a thickness of 15 nm, were prepared for transmission electron microscopy (TEM) observation such that they still could be switched and characterized electrically after the preparation. The result of these observations in comparison with detailed electrical characterization showed (i) normal behavior for relatively long amorphous marks, resulting in a hyperbolic dependence between SET resistance and SET current, indicating a switching mechanism based on initially long and thin nanoscale crystalline filaments which thicken gradually, and (ii) anomalous behavior, which holds for relatively short amorphous marks, where initially directly a massive crystalline filament is formed that consumes most of the width of the amorphous mark only leaving minor residual amorphous regions at its edges. The present results demonstrate that even in (purposely) thick TEM samples, the TEM sample preparation hampers the probability to observe normal behavior and it can be debated whether it is possible to produce electrically switchable TEM specimen in which the memory cells behave the same as in their original bulk embedded state.

  13. Transmission Electron Microscope In Situ Straining Technique to Directly Observe Defects and Interfaces During Deformation in Magnesium

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Morrow, Benjamin M.; Cerreta, E. K.; McCabe, R. J.; Tomé, C. N.

    2015-05-14

    In-situ straining was used to study deformation behavior of hexagonal close-packed (hcp) metals.Twinning and dislocation motion, both essential to plasticity in hcp materials, were observed.Typically, these processes are characterized post-mortem by examining remnant microstructural features after straining has occurred. By imposing deformation during imaging, direct observation of active deformation mechanisms is possible. This work focuses on straining of structural metals in a transmission electron microscope (TEM), and a recently developed technique that utilizes familiar procedures and equipment to increase ease of experiments. In-situ straining in a TEM presents several advantages over conventional post-mortem characterization, most notably time-resolution of deformation andmore » streamlined identification of active deformation mechanisms. Drawbacks to the technique and applicability to other studies are also addressed. In-situ straining is used to study twin boundary motion in hcp magnesium. A {101¯2} twin was observed during tensile and compressive loading. Twin-dislocation interactions are directly observed. Notably, dislocations are observed to remain mobile, even after multiple interactions with twin boundaries, a result which suggests that Basinki’s dislocation transformation mechanism by twinning is not present in hcp metals. The coupling of in-situ straining with traditional post-mortem characterization yields more detailed information about material behavior during deformation than either technique alone.« less

  14. Atomic-resolution study of polarity reversal in GaSb grown on Si by scanning transmission electron microscopy

    SciTech Connect (OSTI)

    Hosseini Vajargah, S.; Woo, S. Y.; Botton, G. A.; Ghanad-Tavakoli, S.; Kleiman, R. N.; Preston, J. S.

    2012-11-01

    The atomic-resolved reversal of the polarity across an antiphase boundary (APB) was observed in GaSb films grown on Si by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). The investigation of the interface structure at the origin of the APB reveals that coalescence of two domains with Ga-prelayer and Sb-prelayer causes the sublattice reversal. The local strain and lattice rotation distributions of the APB, attributed to the discordant bonding length at the APB with the surrounding GaSb lattice, were further studied using the geometric phase analysis technique. The crystallographic characteristics of the APBs and their interaction with other planar defects were observed with HAADF-STEM. The quantitative agreement between experimental and simulated images confirms the observed polarities in the acquired HAADF-STEM data. The self-annihilation mechanism of the APBs is addressed based on the rotation induced by anti-site bonds and APBs' faceting.

  15. Transmission Electron Microscope In Situ Straining Technique to Directly Observe Defects and Interfaces During Deformation in Magnesium

    SciTech Connect (OSTI)

    Morrow, Benjamin M.; Cerreta, E. K.; McCabe, R. J.; Tom, C. N.

    2015-05-14

    In-situ straining was used to study deformation behavior of hexagonal close-packed (hcp) metals.Twinning and dislocation motion, both essential to plasticity in hcp materials, were observed.Typically, these processes are characterized post-mortem by examining remnant microstructural features after straining has occurred. By imposing deformation during imaging, direct observation of active deformation mechanisms is possible. This work focuses on straining of structural metals in a transmission electron microscope (TEM), and a recently developed technique that utilizes familiar procedures and equipment to increase ease of experiments. In-situ straining in a TEM presents several advantages over conventional post-mortem characterization, most notably time-resolution of deformation and streamlined identification of active deformation mechanisms. Drawbacks to the technique and applicability to other studies are also addressed. In-situ straining is used to study twin boundary motion in hcp magnesium. A {1012} twin was observed during tensile and compressive loading. Twin-dislocation interactions are directly observed. Notably, dislocations are observed to remain mobile, even after multiple interactions with twin boundaries, a result which suggests that Basinkis dislocation transformation mechanism by twinning is not present in hcp metals. The coupling of in-situ straining with traditional post-mortem characterization yields more detailed information about material behavior during deformation than either technique alone.

  16. Imaging individual lanthanum atoms in zeolite Y by scanning transmission electron microscopy: evidence of lanthanum pair sites

    SciTech Connect (OSTI)

    Xu, Pinghong; Lu, Jing; Aydin, C.; Debefve, Louise M.; Browning, Nigel D.; Chen, Cong-Yan; Gates, Bruce C.

    2015-09-01

    Images of La-exchanged NaY zeolite obtained with aberration-corrected scanning transmission electron microscopy (STEM) show that about 80% of the La cations were present as site-isolated species, with the remainder in pair sites. The distance between La cations in the pair sites ranged from 1.44 to 3.84 Å, consistent with the presence of pairs of cations tilted at various angles with respect to the support surface. The actual distance between La cations in the pair sites is inferred to be approximately 3.84 Å, which is shorter than the distance between the nearest Al sites in the zeolite (4.31 Å). The results therefore suggest the presence of dimeric structures of La cations bridged with OH groups, and the presence of such species has been inferred previously on the basis of X-ray photoelectron spectroscopy (W. Grünert, U. Sauerlandt, R. Schlögl, H.G. Karge, J. Phys. Chem., 97 (1993) 1413).

  17. Transmission Electron Microscope In Situ Straining Technique to Directly Observe Defects and Interfaces During Deformation in Magnesium

    SciTech Connect (OSTI)

    Morrow, Benjamin M.; Cerreta, E. K.; McCabe, R. J.; Tomé, C. N.

    2015-05-14

    In-situ straining was used to study deformation behavior of hexagonal close-packed (hcp) metals.Twinning and dislocation motion, both essential to plasticity in hcp materials, were observed.Typically, these processes are characterized post-mortem by examining remnant microstructural features after straining has occurred. By imposing deformation during imaging, direct observation of active deformation mechanisms is possible. This work focuses on straining of structural metals in a transmission electron microscope (TEM), and a recently developed technique that utilizes familiar procedures and equipment to increase ease of experiments. In-situ straining in a TEM presents several advantages over conventional post-mortem characterization, most notably time-resolution of deformation and streamlined identification of active deformation mechanisms. Drawbacks to the technique and applicability to other studies are also addressed. In-situ straining is used to study twin boundary motion in hcp magnesium. A {101¯2} twin was observed during tensile and compressive loading. Twin-dislocation interactions are directly observed. Notably, dislocations are observed to remain mobile, even after multiple interactions with twin boundaries, a result which suggests that Basinki’s dislocation transformation mechanism by twinning is not present in hcp metals. The coupling of in-situ straining with traditional post-mortem characterization yields more detailed information about material behavior during deformation than either technique alone.

  18. Dynamics of electron solvation in methanol: Excited state relaxation and generation by charge-transfer-to-solvent

    SciTech Connect (OSTI)

    Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.

    2015-06-21

    The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism.

  19. Bis(pentamethylcyclopentadienyl) ytterbium: Electron-transfer reactions with organotransition metal complexes

    SciTech Connect (OSTI)

    Matsunaga, P.T.

    1991-11-01

    The divalent lanthanide complex, (Me{sub 5}C{sub 5}){sub 2}Yb, reacts with methylcopper to produce the base-free, ytterbium-methyl complex, (Me{sub 5}C{sub 5}){sub 2}YbMe. This product forms a asymmetric, methyl-bridged dimer in the solid state. The bulky alkyl complex, (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}, displays similar chemistry to (Me{sub 5}C{sub 5}){sub 2}YbMe, but at a reduced reaction rate due to the limited accessibility of the metal in (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}. Copper and silver halide salts react with (Me{sub 5}C{sub 5}){sub 2}V to produce the trivalent halide derivatives, (Me{sub 5}C{sub 5}){sub 2}VX (X + F, Cl, Br, I). The chloride complex, (Me{sub 5}C{sub 5}){sub 2}VCl, reacts with lithium reagents to form the phenyl and borohydride species. Nitrous oxide transfers an oxygen atom to (Me{sub 5}C{sub 5}){sub 2}V producing the vanadium-oxo complex, (Me{sub 5}Ce{sub 5}){sub 2}VO. The trivalent titanium species, (Me{sub 5}C{sub 5}){sub 2}TiX (X = Cl, Br, Me, BH{sub 4}), form bimetallic coordination complexes with (Me{sub 5}C{sub 5}){sub 2}Yb. The magnetic behavior of the products indicates that electron transfer has not occurred. The solid state structures of the chloride and bromide complexes show unusual bend angles for the halide bridges between ytterbium and titanium. A model based on frontier orbital theory has been proposed to account for the bending behavior in these species. The bimetallic methyl complex contains a linear methyl bridge between ytterbium and titanium.

  20. Rational engineering of Geobacter sulfurreducens electron transfer components: A foundation for building improved Geobacter-based bioelectrochemical technologies

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Dantas, Joana M.; Morgado, Leonor; Aklujkar, Muktak; Bruix, Marta; Londer, Yuri Y.; Schiffer, Marianne; Pokkuluri, P. Raj; Salgueiro, Carlos A.

    2015-07-30

    Multiheme cytochromes have been implicated in Geobacter sulfurreducens extracellular electron transfer (EET). These proteins are potential targets to improve EET and enhance bioremediation and electrical current production by G. sulfurreducens. However, the functional characterization of multiheme cytochromes is particularly complex due to the co-existence of several microstates in solution, connecting the fully reduced and fully oxidized states. Throughout the last decade, new strategies have been developed to characterize multiheme redox proteins functionally and structurally. These strategies were used to reveal the functional mechanism of G. sulfurreducens multiheme cytochromes and also to identify key residues in these proteins for EET. Inmore » previous studies, we set the foundations for enhancement of the EET abilities of G. sulfurreducens by characterizing a family of five triheme cytochromes (PpcA-E). These periplasmic cytochromes are implicated in electron transfer between the oxidative reactions of metabolism in the cytoplasm and the reduction of extracellular terminal electron acceptors at the cell's outer surface. The results obtained suggested that PpcA can couple e-/H+ transfer, a property that might contribute to the proton electrochemical gradient across the cytoplasmic membrane for metabolic energy production. The structural and functional properties of PpcA were characterized in detail and used for rational design of a family of 23 single site PpcA mutants. In this review, we summarize the functional characterization of the native and mutant proteins. Mutants that retain the mechanistic features of PpcA and adopt preferential e-/H+ transfer pathways at lower reduction potential values compared to the wild-type protein were selected for in vivo studies as the best candidates to increase the electron transfer rate of G. sulfurreducens. For the first time G. sulfurreducens strains have been manipulated by the introduction of mutant forms of

  1. Electronic-to-vibrational energy transfer from Br* to CO2 and electronic-to-vibrational laser feasibility studies. Master's thesis

    SciTech Connect (OSTI)

    Katapski, S.M.

    1992-11-01

    The energy transfer mechanism from photo-excited bromine atoms (Br(2P sub 1/2)) to C02 is investigated in a pulsed fluorescence experiment. An excimer-pumped pulsed dye laser operating at 480 nm is used to photolyze molecular bromine, resulting in the creation of one excited state bromine atom, Br(2P sub 1/2), and one ground state atom, Br(2P sub 3/2). The electronically-excited bromine atoms (referred to as Br*) collide with and excite vibrational modes in the ground electronic state of CO2. Measurements are made of the Br* lifetimes and associated quenching processes, and the electronic-to-vibrational (E yields V) energy transfer rate from Br* to CO2. The feasibility of subsequent stimulated emission from the CO2 on the (101)-(100)(4.3 micron) transition is studied, and attempts are made to achieve lasing. Limitations of the experimental apparatus prevented achieving stimulated emission on the 4.3 micron transition. Recommendations are made for improvements in the analysis and apparatus for further research.... Bromine, Spin-orbit relaxation, Quenching, E-V energy transfer.

  2. Infrared fluorescence studies of electronic-to-vibrational energy transfer in a Br2:NO system. Master's thesis

    SciTech Connect (OSTI)

    Hawks, M.R.

    1993-12-01

    Steady-state photolysis techniques were used to study electronic-to-vibrational energy transfer mechanisms from atomic bromine to nitric oxide. Molecular bromine was photodissociated by 488nm radiation to produce equal parts Br(2p(sub 1/2)) and Br(2p (sub 3/2)). Side fluorescence intensity from Br(2p (sub 1/2)) at 2.7 microns and from NO (v =1) and 2 around 5.3 microns measured as a function of bromine pressure and nitric oxide pressure. The branching ratio collisional transfer into the first and second states of NO was determined, and previously reported rates for quenching of NO by molecular bromine were verified. Nitric oxide, Bromine, E-V transfer, Infrared fluorescence, Photolysis.

  3. Development of a testing method for asbestos fibers in treated materials of asbestos containing wastes by transmission electron microscopy

    SciTech Connect (OSTI)

    Yamamoto, Takashi; Kida, Akiko; Noma, Yukio; Terazono, Atsushi; Sakai, Shin-ichi

    2014-02-15

    Highlights: • A high sensitive and selective testing method for asbestos in treated materials of asbestos containing wastes was developed. • Asbestos can be determined at a limits are a few million fibers per gram and a few μg g{sup −1}. • High temperature melting treatment samples were determined by this method. Asbestos fiber concentration were below the quantitation limit in all samples, and total fiber concentrations were determined as 47–170 × 10{sup 6} g{sup −1}. - Abstract: Appropriate treatment of asbestos-containing wastes is a significant problem. In Japan, the inertization of asbestos-containing wastes based on new treatment processes approved by the Minister of the Environment is promoted. A highly sensitive method for testing asbestos fibers in inertized materials is required so that these processes can be approved. We developed a method in which fibers from milled treated materials are extracted in water by shaking, and are counted and identified by transmission electron microscopy. Evaluation of this method by using asbestos standards and simulated slag samples confirmed that the quantitation limits are a few million fibers per gram and a few μg/g in a sample of 50 mg per filter. We used this method to assay asbestos fibers in slag samples produced by high-temperature melting of asbestos-containing wastes. Fiber concentrations were below the quantitation limit in all samples, and total fiber concentrations were determined as 47–170 × 10{sup −6} f/g. Because the evaluation of treated materials by TEM is difficult owing to the limited amount of sample observable, this testing method should be used in conjunction with bulk analytical methods for sure evaluation of treated materials.

  4. Rapid Laser Induced Crystallization of Amorphous NiTi Films Observed by Nanosecond Dynamic Transmission Electron Microscopy (DTEM)

    SciTech Connect (OSTI)

    LaGrange, T; Campbell, G H; Browning, N D; Reed, B W; Grummon, D S

    2010-03-01

    The crystallization processes of the as-deposited, amorphous NiTi thin films have been studied in detail using techniques such as differential scanning calorimetry and, in-situ TEM. The kinetic data have been analyzed in terms of Johnson-Mehl-Avrami-Kolomogrov (JMAK) semi-empirical formula. The kinetic parameters determined from this analysis have been useful in defining process control parameters for tailoring microstructural features and shape memory properties. Due to the commercial push to shrink thin film-based devices, unique processing techniques have been developed using laser-based annealing to spatially control the microstructure evolution down to sub-micron levels. Nanosecond, pulse laser annealing is particularly attractive since it limits the amount of peripheral heating and unwanted microstructural changes to underlying or surrounding material. However, crystallization under pulsed laser irradiation can differ significantly from conventional thermal annealing, e.g., slow heating in a furnace. This is especially true for amorphous NiTi materials and relevant for shape memory thin film based microelectromechanical systems (MEMS) applications. There is little to no data on the crystallization kinetics of NiTi under pulsed laser irradiation, primarily due to the high crystallization rates intrinsic to high temperature annealing and the spatial and temporal resolution limits of standard techniques. However, with the high time and spatial resolution capabilities of the dynamic transmission electron microscope (DTEM) constructed at Lawrence Livermore National Laboratory, the rapid nucleation events occurring from pulsed laser irradiation can be directly observed and nucleation rates can be quantified. This paper briefly explains the DTEM approach and how it used to investigate the pulsed laser induced crystallization processes in NiTi and to determine kinetic parameters.

  5. Semiclassical Green’s functions and an instanton formulation of electron-transfer rates in the nonadiabatic limit

    SciTech Connect (OSTI)

    Richardson, Jeremy O. Bauer, Rainer; Thoss, Michael

    2015-10-07

    We present semiclassical approximations to Green’s functions of multidimensional systems, extending Gutzwiller’s work to the classically forbidden region. Based on steepest-descent integrals over these functions, we derive an instanton method for computing the rate of nonadiabatic reactions, such as electron transfer, in the weak-coupling limit, where Fermi’s golden-rule can be employed. This generalizes Marcus theory to systems for which the environment free-energy curves are not harmonic and where nuclear tunnelling plays a role. The derivation avoids using the Im F method or short-time approximations to real-time correlation functions. A clear physical interpretation of the nuclear tunnelling processes involved in an electron-transfer reaction is thus provided. In Paper II [J. O. Richardson, J. Chem. Phys. 143, 134116 (2015)], we discuss numerical evaluation of the formulae.

  6. Application of Momentum Transfer Theory for Ion and Electron Transport in Pure Gases and in Gas Mixtures

    SciTech Connect (OSTI)

    Jovanovic, J.V.; Vrhovac, S. B.

    2004-12-01

    In this paper we have presented two applications of Momentum Transfer Theory (MTT), which were both aimed at obtaining reliable data for modeling of non-equilibrium plasma. Transport properties of ion swarms in presence of Resonant Charge Transfer (RCT) collisions are studied using Momentum Transfer Theory (MTT). Using the developed MTT we tested a previously available anisotropic set of cross-sections for Ar++Ar collisions bay making the comparisons with the available data for the transverse diffusion coefficient. We also developed an anisotropic set of Ne++Ne integral cross-sections based on the available data for mobility, longitudinal and transverse diffusion. Anisotropic sets of cross-sections are needed for Monte Carlo simulations of ion transport and plasma models. Application of Blanc's Law for drift velocities of electrons and ions in gas mixtures at arbitrary reduced electric field strengths E/n0 was studied theoretically and by numerical examples. Corrections for Blanc's Law that include effects of inelastic collisions were derived. In addition we have derived the common mean energy procedure that was proposed by Chiflikian in a general case both for ions and electrons. Both corrected common E/n0 and common mean energy procedures provide excellent results even for electrons at moderate E/n0 where application of Blanc's Law was regarded as impossible. In mixtures of two gases that have negative differential conductivity (NDC) even when neither of the two pure gases show NDC the Blanc's Law procedure was able to give excellent predictions.

  7. Direct observation of electron transfer across a lipid bilayer: laser photolysis of an asymmetric vesicle system containing chlorophyll, methyl viologen, and EDTA

    SciTech Connect (OSTI)

    Ford, W.E.; Tollin, G.

    1980-01-01

    Electron transfer across lipid bilayer vesicle walls was examined by laser flash photolysis to determine the mechanisms of charge transport across the membrane. The discussion is restricted to vesicles whose walls contain phosphatidylcholine, chlorophyll a, and valinomycin. (ACR)

  8. Sulfur oxidation to sulfate coupled with electron transfer to electrodes by Desulfuromonas strain TZ1

    SciTech Connect (OSTI)

    Zhang, T; Bain, TS; Barlett, MA; Dar, SA; Snoeyenbos-West, OL; Nevin, KP; Lovley, DR

    2014-01-02

    Microbial oxidation of elemental sulfur with an electrode serving as the electron acceptor is of interest because this may play an important role in the recovery of electrons from sulfidic wastes and for current production in marine benthic microbial fuel cells. Enrichments initiated with a marine sediment inoculum, with elemental sulfur as the electron donor and a positively poised (+300 mV versus Ag/AgCl) anode as the electron acceptor, yielded an anode biofilm with a diversity of micro-organisms, including Thiobacillus, Sulfurimonas, Pseudomonas, Clostridium and Desulfuromonas species. Further enrichment of the anode biofilm inoculum in medium with elemental sulfur as the electron donor and Fe(III) oxide as the electron acceptor, followed by isolation in solidified sulfur/Fe(III) medium yielded a strain of Desulfuromonas, designated strain TZ1. Strain TZ1 effectively oxidized elemental sulfur to sulfate with an anode serving as the sole electron acceptor, at rates faster than Desulfobulbus propionicus, the only other organism in pure culture previously shown to oxidize S with current production. The abundance of Desulfuromonas species enriched on the anodes of marine benthic fuel cells has previously been interpreted as acetate oxidation driving current production, but the results presented here suggest that sulfur-driven current production is a likely alternative.

  9. A trans-outer membrane porin-cytochrome protein complex for extracellular electron transfer by Geobacter sulfurreducens PCA

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Liu, Yimo; Wang, Zheming; Liu, Juan; Levar, Caleb; Edwards, Marcus; Babauta, Jerome T.; Kennedy, David W.; Shi, Zhi; Beyenal, Haluk; Bond, Daniel R.; et al

    2014-09-24

    The multiheme, outer membrane c-type cytochrome (c-Cyt) OmcB of Geobacter sulfurreducens was previously proposed to mediate electron transfer across the outer membrane. However, the underlying mechanism has remained uncharacterized. In G. sulfurreducens, the omcB gene is part of two tandem four-gene clusters, each is predicted to encode a transcriptional factor (OrfR/OrfS), a porin-like outer membrane protein (OmbB/OmbC), a periplasmic c-type cytochrome (OmaB/OmaC), and an outer membrane c-Cyt (OmcB/OmcC), respectively. Here we showed that OmbB/OmbC, OmaB/OmaC and OmcB/OmcC of G. sulfurreducens PCA formed the porin-cytochrome (Pcc) protein complexes, which were involved in transferring electrons across the outer membrane. The isolated Pccmore » protein complexes reconstituted in proteoliposomes transferred electrons from reduced methyl viologen across the lipid bilayer of liposomes to Fe(III)-citrate and ferrihydrite. The pcc clusters were found in all eight sequenced Geobacter and 11 other bacterial genomes from six different phyla, demonstrating a widespread distribution of Pcc protein complexes in phylogenetically diverse bacteria. Deletion of ombB-omaB-omcB-orfS-ombC-omaC-omcC gene clusters had no impact on the growth of G. sulfurreducens PCA with fumarate, but diminished the ability of G. sulfurreducens PCA to reduce Fe(III)-citrate and ferrihydrite. Finally, complementation with the ombB-omaB-omcB gene cluster restored the ability of G. sulfurreducens PCA to reduce Fe(III)-citrate and ferrihydrite.« less

  10. Probing the nature of electron transfer in metalloproteins on graphene-family materials as nanobiocatalytic scaffold using electrochemistry

    SciTech Connect (OSTI)

    Gupta, Sanju; Irihamye, Aline

    2015-03-15

    Graphene-based nanomaterials have shown great promise not only in nanoelectronics due to ultrahigh electron mobility but also as biocatalytic scaffolds owing to irreversible protein surface adsorption and facilitating direct electron transfer. In this work, we synthesized stable dispersions of graphene using liquid-phase exfoliation approach based on non-covalent interactions between graphene and 1-pyrenesulfonic acid sodium salt (Py–1SO{sub 3}), 1-pyrenemethylamine salt (Py − Me-NH{sub 2}) and Pluronic{sup ®} P-123 surfactant using only water as solvent compatible with biomolecules. The resulting graphene nanoplatelets (Gr-LPE) are characterized by a combination of analytical (microscopy and spectroscopy) techniques revealing mono- to few-layer graphene displaying that the exfoliation efficiency strongly depends upon the type of pyrene-based salts and organic surfactants. Moreover being completely water-based approach, we build robust nanoscaffolds of graphene-family nanomaterials (GFNs) namely, monolayer graphene, Gr-LPE (the one prepared with Pluronic{sup ®} P-123), graphene oxide (GO) and its reduced form (rGO) on glassy carbon electrode surface with three important metalloproteins include cytochrome c (Cyt c) [for electron transfer], myoglobin (Mb) [for oxygen storage] and horseradish peroxidase (HRP) [for catalyzing the biochemical reaction]. In order to demonstrate the nanobiocatalytical activity of these proteins, we used electrochemical interfacial direct electron transfer (DET) kinetics and attempt to determine the rate constant (k{sub ET}) using two different analytical approaches namely, linear sweep voltammetry and Laviron’s theory. We elucidated that all of the metalloproteins retain their structural integrity (secondary structure) upon forming mixtures with GFNs confirmed through optical and vibrational spectroscopy and biological activity using electrochemistry. Among the GFNs studied, Gr-LPE, GO and rGO support the efficient electrical

  11. NREL: Measurements and Characterization - Transmission/Scanning

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Transmission Electron Microscopy Transmission/Scanning Transmission Electron Microscopy In transmission electron microscopy (TEM), a thin sample, typically less than 200 nm, is bombarded by a highly focused beam of single-energy electrons. The beam has enough energy for the electrons to be transmitted through the sample, and the transmitted or scattered electron signal is greatly magnified by a series of electromagnetic lenses. The magnified signal may be observed by electron diffraction,

  12. Enhanced charge transfer to molecular ions by electronic excitation of the target

    SciTech Connect (OSTI)

    Bruckmeier, R.; Wunderlich, C.; Figger, H.

    1995-07-01

    A beam of molecular ions (ArH{sup +}, ArD{sup +}, or D{sub 3}{sup +}) was neutralized by passage through an excited cesium vapor; two single-mode diode lasers were used to populate the 6 {sup 2}{ital P}{sub 3/2} state of the cesium atoms. The charge-transfer cross section could be increased by laser excitation of the Cs target, in some cases by orders of magnitude. This was established by observing the intensity of the luminescence from the neutralized molecules, which was enhanced by a factor of up to 10. The enhancement factors are in qualitative agreement with results of computations that follow the theoretical treatment for atoms introduced by Rapp and Francis [J. Chem. Phys. 37, 2631 (1962)]. This experimental technique is a generally applicable method for any molecular-beam technique that relies on charge transfer.

  13. Communication: Microsecond dynamics of the protein and water affect electron transfer in a bacterial bc{sub 1} complex

    SciTech Connect (OSTI)

    Martin, Daniel R.; Matyushov, Dmitry V.

    2015-04-28

    Cross-membrane electron transport between cofactors localized in proteins of mitochondrial respiration and bacterial photosynthesis is the source of all biological energy. The statistics and dynamics of nuclear fluctuations in these protein/membrane/water heterogeneous systems are critical for their energetic efficiency. The results of 13 ?s of atomistic molecular dynamics simulations of the membrane-bound bc{sub 1} bacterial complex are analyzed here. The reaction is affected by a broad spectrum of nuclear modes, with the slowest dynamics in the range of time-scales ?0.1-1.6 ?s contributing half of the reaction reorganization energy. Two reorganization energies are required to describe protein electron transfer due to dynamical arrest of protein conformations on the observation window. This mechanistic distinction allows significant lowering of activation barriers for reactions in proteins.

  14. Blinking suppression of CdTe quantum dots on epitaxial graphene and the analysis with Marcus electron transfer

    SciTech Connect (OSTI)

    Hirose, Takuya; Tamai, Naoto, E-mail: tamai@kwansei.ac.jp [Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337 (Japan); Kutsuma, Yasunori; Kurita, Atsusi; Kaneko, Tadaaki [Department of Physics, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337 (Japan)

    2014-08-25

    We have prepared epitaxial graphene by a Si sublimation method from 4H-SiC. Single-particle spectroscopy of CdTe quantum dots (QDs) on epitaxial graphene covered with polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG) showed the suppression of luminescence blinking and ?10 times decreased luminescence intensity as compared with those on a glass. The electronic coupling constant, H{sub 01}, between CdTe QDs and graphene was calculated to be (3.3??0.4)??10{sup 2?}cm{sup ?1} in PVP and (3.7??0.8)??10{sup 2?}cm{sup ?1} in PEG based on Marcus theory of electron transfer and Tang-Marcus model of blinking with statistical distribution.

  15. Electron transfer activation of a second water channel for proton transport in [FeFe]-hydrogenase

    SciTech Connect (OSTI)

    Sode, Olaseni; Voth, Gregory A.

    2014-12-14

    Hydrogenase enzymes are important because they can reversibly catalyze the production of molecular hydrogen. Proton transport mechanisms have been previously studied in residue pathways that lead to the active site of the enzyme via residues Cys299 and Ser319. The importance of this pathway and these residues has been previously exhibited through site-specific mutations, which were shown to interrupt the enzyme activity. It has been shown recently that a separate water channel (WC2) is coupled with electron transport to the active site of the [FeFe]-hydrogenase. The water-mediated proton transport mechanisms of the enzyme in different electronic states have been studied using the multistate empirical valence bond reactive molecular dynamics method, in order to understand any role WC2 may have in facilitating the residue pathway in bringing an additional proton to the enzyme active site. In a single electronic state A{sup 2?}, a water wire was formed through which protons can be transported with a low free energy barrier. The remaining electronic states were shown, however, to be highly unfavorable to proton transport in WC2. A double amino acid substitution is predicted to obstruct proton transport in electronic state A{sup 2-} by closing a cavity that could otherwise fill with water near the proximal Fe of the active site.

  16. Role of Quinones in Electron Transfer of PQQ–Glucose Dehydrogenase Anodes—Mediation or Orientation Effect

    SciTech Connect (OSTI)

    Babanova, Sofia; Matanovic, Ivana; Chavez, Madelaine Seow; Atanassov, Plamen

    2015-06-24

    In this study, the influence of two quinones (1,2- and 1,4-benzoquinone) on the operation and mechanism of electron transfer in PQQ-dependent glucose dehydrogenase (PQQ–sGDH) anodes has been determined. Benzoquinones were experimentally explored as mediators present in the electrolyte. The electrochemical performance of the PQQ–sGDH anodes with and without the mediators was examined and for the first time molecular docking simulations were used to gain a fundamental understanding to explain the role of the mediator molecules in the design and operation of the enzymatic electrodes. It was proposed that the higher performance of the PQQ–sGDH anodes in the presence of 1,2- and 1,4-benzoquinones introduced in the solution is due to the shorter distance between these molecules and PQQ in the enzymatic molecule. It was also hypothesized that when 1,4-benzoquinone is adsorbed on a carbon support, it would play the dual role of a mediator and an orienting agent. At the same time, when 1,2-benzoquinone and ubiquinone are adsorbed on the electrode surface, the enzyme would transfer the electrons directly to the support, and these molecules would primarily play the role of an orienting agent.

  17. Role of quinones in electron transfer of PQQ–glucose dehydrogenase anodes—mediation or orientation effect

    SciTech Connect (OSTI)

    Babanova, Sofia; Matanovic, Ivana; Chavez, Madelaine Seow; Atanassov, Plamen

    2015-06-16

    In this study, the influence of two quinones (1,2- and 1,4-benzoquinone) on the operation and mechanism of electron transfer in PQQ-sGDH anodes has been determined. Benzoquinones were experimentally explored as mediators present in the electrolyte. The electrochemical performance of the PQQ–sGDH anodes with and without the mediators was examined and for the first time molecular docking simulations were used to gain a fundamental understanding to explain the role of the mediator molecules in the design and operation of the enzymatic electrodes. It was proposed that the higher performance of the PQQ–sGDH anodes in the presence of 1,2- and 1,4-benzoquinones introduced in the solution is due to the shorter distance between these molecules and PQQ in the enzymatic molecule. It was also hypothesized that when 1,4-benzoquinone is adsorbed on a carbon support, it would play the dual role of a mediator and an orienting agent. At the same time, when 1,2-benzoquinone and ubiquinone are adsorbed on the electrode surface, the enzyme would transfer the electrons directly to the support, and these molecules would primarily play the role of an orienting agent.

  18. Role of quinones in electron transfer of PQQ–glucose dehydrogenase anodes—mediation or orientation effect

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Babanova, Sofia; Matanovic, Ivana; Chavez, Madelaine Seow; Atanassov, Plamen

    2015-06-16

    In this study, the influence of two quinones (1,2- and 1,4-benzoquinone) on the operation and mechanism of electron transfer in PQQ-sGDH anodes has been determined. Benzoquinones were experimentally explored as mediators present in the electrolyte. The electrochemical performance of the PQQ–sGDH anodes with and without the mediators was examined and for the first time molecular docking simulations were used to gain a fundamental understanding to explain the role of the mediator molecules in the design and operation of the enzymatic electrodes. It was proposed that the higher performance of the PQQ–sGDH anodes in the presence of 1,2- and 1,4-benzoquinones introducedmore » in the solution is due to the shorter distance between these molecules and PQQ in the enzymatic molecule. It was also hypothesized that when 1,4-benzoquinone is adsorbed on a carbon support, it would play the dual role of a mediator and an orienting agent. At the same time, when 1,2-benzoquinone and ubiquinone are adsorbed on the electrode surface, the enzyme would transfer the electrons directly to the support, and these molecules would primarily play the role of an orienting agent.« less

  19. Final Report: The Impact of Carbonate on Surface Protonation, Electron Transfer and Crystallization Reactions in Iron Oxide Nanoparticles and Colloids

    SciTech Connect (OSTI)

    Dixon, David Adams

    2013-07-02

    This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

  20. Role of quinones in electron transfer of PQQglucose dehydrogenase anodesmediation or orientation effect

    SciTech Connect (OSTI)

    Babanova, Sofia; Matanovic, Ivana; Chavez, Madelaine Seow; Atanassov, Plamen

    2015-06-16

    In this study, the influence of two quinones (1,2- and 1,4-benzoquinone) on the operation and mechanism of electron transfer in PQQ-sGDH anodes has been determined. Benzoquinones were experimentally explored as mediators present in the electrolyte. The electrochemical performance of the PQQsGDH anodes with and without the mediators was examined and for the first time molecular docking simulations were used to gain a fundamental understanding to explain the role of the mediator molecules in the design and operation of the enzymatic electrodes. It was proposed that the higher performance of the PQQsGDH anodes in the presence of 1,2- and 1,4-benzoquinones introduced in the solution is due to the shorter distance between these molecules and PQQ in the enzymatic molecule. It was also hypothesized that when 1,4-benzoquinone is adsorbed on a carbon support, it would play the dual role of a mediator and an orienting agent. At the same time, when 1,2-benzoquinone and ubiquinone are adsorbed on the electrode surface, the enzyme would transfer the electrons directly to the support, and these molecules would primarily play the role of an orienting agent.

  1. GHz laser-free time-resolved transmission electron microscopy: A stroboscopic high-duty-cycle method

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Qiu, Jiaqi; Zhu, Yimei; Ha, Gwanghui; Jing, Chunguang; Baryshev, Sergey V.; Reed, Bryan W.; Lau, June W.

    2015-11-10

    In this study, a device and a method for producing ultrashort electron pulses with GHz repetition rates via pulsing an input direct current (dc) electron beam are provided. The device and the method are based on an electromagnetic-mechanical pulser (EMMP) that consists of a series of transverse deflecting cavities and magnetic quadrupoles. The EMMP modulates and chops the incoming dc electron beam and converts it into pico- and sub-pico-second electron pulse sequences (pulse trains) at >1 GHz repetition rates, as well as controllably manipulates the resulting pulses. Ultimately, it leads to negligible electron pulse phase-space degradation compared to the incomingmore » dc beam parameters. The temporal pulse length and repetition rate for the EMMP can be continuously tunable over wide ranges.« less

  2. GHz laser-free time-resolved transmission electron microscopy: A stroboscopic high-duty-cycle method

    SciTech Connect (OSTI)

    Qiu, Jiaqi; Zhu, Yimei; Ha, Gwanghui; Jing, Chunguang; Baryshev, Sergey V.; Reed, Bryan W.; Lau, June W.

    2015-11-10

    In this study, a device and a method for producing ultrashort electron pulses with GHz repetition rates via pulsing an input direct current (dc) electron beam are provided. The device and the method are based on an electromagnetic-mechanical pulser (EMMP) that consists of a series of transverse deflecting cavities and magnetic quadrupoles. The EMMP modulates and chops the incoming dc electron beam and converts it into pico- and sub-pico-second electron pulse sequences (pulse trains) at >1 GHz repetition rates, as well as controllably manipulates the resulting pulses. Ultimately, it leads to negligible electron pulse phase-space degradation compared to the incoming dc beam parameters. The temporal pulse length and repetition rate for the EMMP can be continuously tunable over wide ranges.

  3. High resolution low dose transmission electron microscopy real-time imaging and manipulation of nano-scale objects in the electron beam

    DOE Patents [OSTI]

    Brown, Jr., R. Malcolm; Barnes, Zack; Sawatari, Chie; Kondo, Tetsuo

    2008-02-26

    The present invention includes a method, apparatus and system for nanofabrication in which one or more target molecules are identified for manipulation with an electron beam and the one or more target molecules are manipulated with the electron beam to produce new useful materials.

  4. Two-center interference in fast proton-H{sub 2}-electron transfer and excitation processes

    SciTech Connect (OSTI)

    Stoechkel, K.; Eidem, O.; Cederquist, H.; Zettergren, H.; Reinhed, P.; Schuch, R.; Schmidt, H. T.; Cocke, C. L.; Levin, S. B.; Ostrovsky, V. N.; Kaelberg, A.; Simonsson, A.; Jensen, J.

    2005-11-15

    We present experimental evidence for a strong dependence on the angle between the molecular axis of H{sub 2} and the direction of the incoming projectile (p) in the cross section for transfer excitation in fast p-H{sub 2} collisions. For collision energies of 1.0 and 1.3 MeV we find good agreement between the observed data and an analytical expression based on a two-atomic-center description using Brinkman-Kramers amplitudes. This clearly shows that the observed angular dependence is a result of quantum mechanical interference and not a trivial geometrical effect.

  5. Nano-scale luminescence characterization of individual InGaN/GaN quantum wells stacked in a microcavity using scanning transmission electron microscope cathodoluminescence

    SciTech Connect (OSTI)

    Schmidt, Gordon Mller, Marcus; Veit, Peter; Bertram, Frank; Christen, Jrgen; Glauser, Marlene; Carlin, Jean-Franois; Cosendey, Gatien; Butt, Raphal; Grandjean, Nicolas

    2014-07-21

    Using cathodoluminescence spectroscopy directly performed in a scanning transmission electron microscope at liquid helium temperatures, the optical and structural properties of a 62 InGaN/GaN multiple quantum well embedded in an AlInN/GaN based microcavity are investigated at the nanometer scale. We are able to spatially resolve a spectral redshift between the individual quantum wells towards the surface. Cathodoluminescence spectral linescans allow directly visualizing the critical layer thickness in the quantum well stack resulting in the onset of plastic relaxation of the strained InGaN/GaN system.

  6. Power Electronics for Distributed Energy Systems and Transmission and Distribution Applications: Assessing the Technical Needs for Utility Applications

    SciTech Connect (OSTI)

    Tolbert, L.M.

    2005-12-21

    Power electronics can provide utilities the ability to more effectively deliver power to their customers while providing increased reliability to the bulk power system. In general, power electronics is the process of using semiconductor switching devices to control and convert electrical power flow from one form to another to meet a specific need. These conversion techniques have revolutionized modern life by streamlining manufacturing processes, increasing product efficiencies, and increasing the quality of life by enhancing many modern conveniences such as computers, and they can help to improve the delivery of reliable power from utilities. This report summarizes the technical challenges associated with utilizing power electronics devices across the entire spectrum from applications to manufacturing and materials development, and it provides recommendations for research and development (R&D) needs for power electronics systems in which the U.S. Department of Energy (DOE) could make a substantial impact toward improving the reliability of the bulk power system.

  7. Nanowires, Capacitors, and Other Novel Outer-Surface Components Involved in Electron Transfer to Fe(III) Oxides in Geobacter Species

    SciTech Connect (OSTI)

    Lovley, Derek, R.

    2008-12-22

    The overall goal of this project was to better understand the mechanisms by which Geobacter species transfer electrons outside the cell onto Fe(III) oxides. The rationale for this study was that Geobacter species are often the predominant microorganisms involved in in situ uranium bioremediation and the growth and activity of the Geobacter species during bioremediation is primarily supported by electron transfer to Fe(III) oxides. These studies greatly expanded the understanding of electron transfer to Fe(III). Novel concepts developed included the potential role of microbial nanowires for long range electron transfer in Geobacter species and the importance of extracytoplasmic cytochromes functioning as capacitors to permit continued electron transfer during the hunt for Fe(III) oxide. Furthermore, these studies provided target sequences that were then used in other studies to tract the activity of Geobacter species in the subsurface through monitoring the abundance of gene transcripts of the target genes. A brief summary of the major accomplishments of the project is provided.

  8. Ensemble density functional theory method correctly describes bond dissociation, excited state electron transfer, and double excitations

    SciTech Connect (OSTI)

    Filatov, Michael; Huix-Rotllant, Miquel; Burghardt, Irene

    2015-05-14

    State-averaged (SA) variants of the spin-restricted ensemble-referenced Kohn-Sham (REKS) method, SA-REKS and state-interaction (SI)-SA-REKS, implement ensemble density functional theory for variationally obtaining excitation energies of molecular systems. In this work, the currently existing version of the SA-REKS method, which included only one excited state into the ensemble averaging, is extended by adding more excited states to the averaged energy functional. A general strategy for extension of the REKS-type methods to larger ensembles of ground and excited states is outlined and implemented in extended versions of the SA-REKS and SI-SA-REKS methods. The newly developed methods are tested in the calculation of several excited states of ground-state multi-reference systems, such as dissociating hydrogen molecule, and excited states of donor–acceptor molecular systems. For hydrogen molecule, the new method correctly reproduces the distance dependence of the lowest excited state energies and describes an avoided crossing between the doubly excited and singly excited states. For bithiophene–perylenediimide stacked complex, the SI-SA-REKS method correctly describes crossing between the locally excited state and the charge transfer excited state and yields vertical excitation energies in good agreement with the ab initio wavefunction methods.

  9. Transmission Planning Analysis Tool

    SciTech Connect (OSTI)

    2015-06-23

    Developed to solve specific problem: Assist transmission planning for regional transfers in interconnected power systems. This work was originated in a study for the U.S. Department of State, to recommend transmission reinforcements for the Central American regional system that interconnects 6 countries. Transmission planning analysis is currently performed by engineers with domainspecific and systemspecific knowledge without a unique methodology. The software codes of this disclosure assists engineers by defining systematic analysis procedures to help identify weak points and make decisions on transmission planning of regional interconnected power systems. Transmission Planning Analysis Tool groups PSS/E results of multiple AC contingency analysis and voltage stability analysis and QV analysis of many scenarios of study and arrange them in a systematic way to aid power system planning engineers or transmission operators in effective decision]making process or in the off]line study environment.

  10. Transmission Planning Analysis Tool

    Energy Science and Technology Software Center (OSTI)

    2015-06-23

    Developed to solve specific problem: Assist transmission planning for regional transfers in interconnected power systems. This work was originated in a study for the U.S. Department of State, to recommend transmission reinforcements for the Central American regional system that interconnects 6 countries. Transmission planning analysis is currently performed by engineers with domainspecific and systemspecific knowledge without a unique methodology. The software codes of this disclosure assists engineers by defining systematic analysis procedures to help identifymore » weak points and make decisions on transmission planning of regional interconnected power systems. Transmission Planning Analysis Tool groups PSS/E results of multiple AC contingency analysis and voltage stability analysis and QV analysis of many scenarios of study and arrange them in a systematic way to aid power system planning engineers or transmission operators in effective decision]making process or in the off]line study environment.« less

  11. More stable hybrid organic solar cells deposited on amorphous Si electron transfer layer

    SciTech Connect (OSTI)

    Samiee, Mehran; Modtland, Brian; Dalal, Vikram L.; Aidarkhanov, Damir

    2014-05-26

    We report on defect densities, performance, and stability of organic/inorganic hybrid solar cells produced using n-doped inorganic amorphous silicon-carbide layers as the electron transport layer (ETL). The organic material was poly-3-hexyl-thiophene (P3HT) and heterojunction was formed using phenyl-C{sub 71}-Butyric-Acid-Methyl Ester (PCBM). For comparison, inverted solar cells fabricated using Cs{sub 2}CO{sub 3} as ETL were fabricated. Defect densities and subgap quantum efficiency curves were found to be nearly identical for both types of cells. The cells were subjected to 2xsun illumination and it was found that the cells produced using doped a-Si as ETL were much more stable than the cells produced using Cs{sub 2}CO{sub 3}.

  12. Transition Metal Donor-Peptide-Acceptor Complexes: From Intramolecular Electron Transfer Reactions to the Study of Reactive Intermediates

    SciTech Connect (OSTI)

    Isied, Stephan S.

    2003-03-11

    The trans-polyproline (PII) oligomers (Figure 1) are unusually rigid peptide structures which have been extensively studied by our group for peptide mediated intramolecular electron transfer (ET) at long distances. We have previously studied ET across a series of metal ion donor (D) acceptor (A) oligoproline peptides with different distances, driving forces and reorganizational energies. The majority of these experiments involve generating the ET intermediate using pulse radiolysis methods, although more recently photochemical methods are also used. Results of these studies showed that ET across peptides can vary by more than twelve orders of magnitude. Using ruthenium bipyridine donors, ET reaction rate constants across several proline residues (n = 4 - 9) occurred in the millisecond (ms) to {micro}s timescale, thus limiting the proline peptide conformational motions to only minor changes (far smaller than the large changes that occur on the ms to sec timescale, such as trans to cis proline isomerization). The present report describes our large data base of experimental results for D-peptide-A complexes in terms of a model where the involvement of both superexchange and hopping (hole and electron) mechanisms account for the long range ET rate constants observed. Our data shows that the change from superexchange to hopping mechanisms occurs at different distances depending on the type of D and A and their interactions with the peptides. Our model is also consistent with generalized models for superexchange and hopping which have been put forward by a number of theoretical groups to account for long range ET phenomena.

  13. Electronic Coupling Dependence of Ultrafast Interfacial Electron...

    Office of Scientific and Technical Information (OSTI)

    Electron Transfer on Nanocrystalline Thin Films and Single Crystal Lian, Tianquan 14 SOLAR ENERGY The long-term goal of the proposed research is to understand electron transfer...

  14. Atomic arrangement at ZnTe/CdSe interfaces determined by high resolution scanning transmission electron microscopy and atom probe tomography

    SciTech Connect (OSTI)

    Bonef, Bastien; Rouvire, Jean-Luc; Jouneau, Pierre-Henri; Bellet-Amalric, Edith; Grard, Lionel; Mariette, Henri; Andr, Rgis; Bougerol, Catherine; Grenier, Adeline

    2015-02-02

    High resolution scanning transmission electron microscopy and atom probe tomography experiments reveal the presence of an intermediate layer at the interface between two binary compounds with no common atom, namely, ZnTe and CdSe for samples grown by Molecular Beam Epitaxy under standard conditions. This thin transition layer, of the order of 1 to 3 atomic planes, contains typically one monolayer of ZnSe. Even if it occurs at each interface, the direct interface, i.e., ZnTe on CdSe, is sharper than the reverse one, where the ZnSe layer is likely surrounded by alloyed layers. On the other hand, a CdTe-like interface was never observed. This interface knowledge is crucial to properly design superlattices for optoelectronic applications and to master band-gap engineering.

  15. A transmission electron microscopy study of the deformation behavior underneath nanoindents in nano-scale Al-TiN multilayered composites

    SciTech Connect (OSTI)

    Bhattacharyya, Dhriti; Mara, Nathan A; Dickerson, Patricia O; Misra, Amit; Hoagland, R G

    2009-01-01

    Nano-scale multilayered Al-TiN composites were deposited with DC magnetron sputtering technique in two different layer thickness ratios - Al:TiN = 1:1 and Al:TiN = 9:1. The Al layer thickness varied from 2 nm to 450 nm. The hardness of the samples was tested by nanoindentation using a Berkovich tip. Cross-sectional Transmission Electron Microscopy (TEM) was carried out on samples extracted with Focused Ion Beam (FIB) from below the nanoindents. This paper presents the results of the hardness tests in the Al-TiN multilayers with the two different thickness ratios and the observations from the cross-sectional TEM studies of the regions underneath the indents. These studies showed remarkable strength in the multilayers, as well as some very interesting deformation behavior in the TiN layers at extremely small length scales, where the hard TiN layers undergo co-deformation with the Al layers.

  16. EXTRACTION OF FRACTURE-MECHANICS AND TRANSMISSION-ELECTRON-MICROSCOPY SAMPLES FROM TRITIUM-EXPOSED RESERVOIRS USING ELECTRIC-DISCHARGE MACHINING

    SciTech Connect (OSTI)

    Morgan, M; Ken Imrich, K; Michael Tosten, M

    2006-08-31

    The Enhanced Surveillance Campaign is funding a program to investigate tritium aging effects on the structural properties of tritium reservoir steels. The program is designed to investigate how the structural properties of reservoir steels change during tritium service and to examine the role of microstructure and reservoir manufacturing on tritium compatibility. New surveillance tests are also being developed that can better gauge the long-term effects of tritium and its radioactive decay product, helium-3, on the properties of reservoir steels. In order to conduct these investigations, three types of samples are needed from returned reservoirs: tensile, fracture mechanics, and transmission-electron microscopy (TEM). An earlier report demonstrated how the electric-discharge machining (EDM) technique can be used for cutting tensile samples from serial sections of a 3T reservoir and how yield strength, ultimate strength and elongation could be measured from those samples. In this report, EDM was used successfully to section sub-sized fracture-mechanics samples from the inner and outer walls of a 3T reservoir and TEM samples from serial sections of a 1M reservoir. This report fulfills the requirements for the FY06 Level 3 milestone, TSR 15.1 ''Cut Fracture-Mechanics Samples from Tritium-Exposed Reservoir'' and TSR 15.2 ''Cut Transmission-electron-microscopy foils from Tritium-Exposed Reservoir'' for the Enhance Surveillance Campaign (ESC). This was in support of ESC L2-1870 Milestone-''Provide aging and lifetime assessments of selected components and materials for multiple enduring stockpile systems''.

  17. Determination of crystal growth rates during rapid solidification of polycrystalline aluminum by nano-scale spatio-temporal resolution in situ transmission electron microscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Zweiacker, K.; McKeown, J. T.; Liu, C.; LaGrange, T.; Reed, B. W.; Campbell, G. H.; Wiezorek, J. M. K.

    2016-08-04

    In situ investigations of rapid solidification in polycrystalline Al thin films were conducted using nano-scale spatio-temporal resolution dynamic transmission electron microscopy. Differences in crystal growth rates and asymmetries in melt pool development were observed as the heat extraction geometry was varied by controlling the proximity of the laser-pulse irradiation and the associated induced melt pools to the edge of the transmission electron microscopy support grid, which acts as a large heat sink. Experimental parameters have been established to maximize the reproducibility of the material response to the laser-pulse-related heating and to ensure that observations of the dynamical behavior of themore » metal are free from artifacts, leading to accurate interpretations and quantifiable measurements with improved precision. Interface migration rate measurements revealed solidification velocities that increased consistently from ~1.3 m s–1 to ~2.5 m s–1 during the rapid solidification process of the Al thin films. Under the influence of an additional large heat sink, increased crystal growth rates as high as 3.3 m s–1 have been measured. The in situ experiments also provided evidence for development of a partially melted, two-phase region prior to the onset of rapid solidification facilitated crystal growth. As a result, using the experimental observations and associated measurements as benchmarks, finite-element modeling based calculations of the melt pool evolution after pulsed laser irradiation have been performed to obtain estimates of the temperature evolution in the thin films.« less

  18. A method for measuring the local gas pressure within a gas-flow stage in situ in the transmission electron microscope

    SciTech Connect (OSTI)

    Colby, Robert J.; Alsem, Daan H.; Liyu, Andrey V.; Kabius, Bernd C.

    2015-06-01

    The development of environmental transmission electron microscopy (TEM) has enabled in situ experiments in a gaseous environment with high resolution imaging and spectroscopy. Addressing scientific challenges in areas such as catalysis, corrosion, and geochemistry can require pressures much higher than the ~20 mbar achievable with a differentially pumped, dedicated environmental TEM. Gas flow stages, in which the environment is contained between two semi-transparent thin membrane windows, have been demonstrated at pressures of several atmospheres. While this constitutes significant progress towards operando measurements, the design of many current gas flow stages is such that the pressure at the sample cannot necessarily be directly inferred from the pressure differential across the system. Small differences in the setup and design of the gas flow stage can lead to very different sample pressures. We demonstrate a method for measuring the gas pressure directly, using a combination of electron energy loss spectroscopy and TEM imaging. This method requires only two energy filtered TEM images, limiting the measurement time to a few seconds and can be performed during an ongoing experiment at the region of interest. This approach provides a means to ensure reproducibility between different experiments, and even between very differently designed gas flow stages.

  19. A kinetic study of plutonium dioxide dissolution in hydrochloric acid using iron (II) as an electron transfer catalyst

    SciTech Connect (OSTI)

    Fife, K.W.

    1996-09-01

    Effective dissolution of plutonium dioxide has traditionally been accomplished by contact with strong nitric acid containing a small amount of fluoride at temperatures of {approximately} 100 C. In spite of these aggressive conditions, PuO{sub 2} dissolution is sometimes incomplete requiring additional contact with the solvent. This work focused on an alternative to conventional dissolution in nitric acid where an electron transfer catalyst, Fe(II), was used in hydrochloric acid. Cyclic voltammetry was employed as an in-situ analytical technique for monitoring the dissolution reaction rate. The plutonium oxide selected for this study was decomposed plutonium oxalate with > 95% of the material having a particle diameter (< 70 {micro}m) as determined by a scanning laser microscopy technique. Attempts to dry sieve the oxide into narrow size fractions prior to dissolution in the HCl-Fe(II) solvent system failed, apparently due to significant interparticle attractive forces. Although sieve splits were obtained, subsequent scanning laser microscopy analysis of the sieve fractions indicated that particle segregation was not accomplished and the individual sieve fractions retained a particle size distribution very similar to the original powder assemblage. This phenomena was confirmed through subsequent dissolution experiments on the various screen fractions which illustrated no difference in kinetic behavior between the original oxide assemblage and the sieve fractions.

  20. Accompanying coordinate expansion and recurrence relation method using a transfer relation scheme for electron repulsion integrals with high angular momenta and long contractions

    SciTech Connect (OSTI)

    Hayami, Masao; Seino, Junji; Nakai, Hiromi

    2015-05-28

    An efficient algorithm for the rapid evaluation of electron repulsion integrals is proposed. The present method, denoted by accompanying coordinate expansion and transferred recurrence relation (ACE-TRR), is constructed using a transfer relation scheme based on the accompanying coordinate expansion and recurrence relation method. Furthermore, the ACE-TRR algorithm is extended for the general-contraction basis sets. Numerical assessments clarify the efficiency of the ACE-TRR method for the systems including heavy elements, whose orbitals have long contractions and high angular momenta, such as f- and g-orbitals.

  1. Catching the role of anisotropic electronic distribution and charge transfer in halogen bonded complexes of noble gases

    SciTech Connect (OSTI)

    Bartocci, Alessio; Cappelletti, David; Pirani, Fernando; Belpassi, Leonardo; Falcinelli, Stefano; Grandinetti, Felice; Tarantelli, Francesco

    2015-05-14

    suggested by the analysis of the experiments actually reflect two chemically meaningful contributions, namely, a stabilizing interaction arising from the anisotropy of the charge distribution around the Cl atom in CCl{sub 4} and a stereospecific electron transfer that occurs at the intermolecular distances mainly probed by the experiments. Our model calculations suggest that the largest effect is for the vertex geometry of CCl{sub 4} while other geometries appear to play a minor to negligible role.

  2. Evaluation of stacking faults and associated partial dislocations in AlSb/GaAs (001) interface by aberration-corrected high-resolution transmission electron microscopy

    SciTech Connect (OSTI)

    Wen, C.; Ge, B. H.; Cui, Y. X.; Li, F. H.; Zhu, J.; Yu, R.; Cheng, Z. Y.

    2014-11-15

    The stacking faults (SFs) in an AlSb/GaAs (001) interface were investigated using a 300 kV spherical aberration-corrected high-resolution transmission electron microscope (HRTEM). The structure and strain distribution of the single and intersecting (V-shaped) SFs associated with partial dislocations (PDs) were characterized by the [110] HRTEM images and geometric phase analysis, respectively. In the biaxial strain maps ?{sub xx} and ?{sub yy}, a SF can be divided into several sections under different strain states (positive or negative strain values). Furthermore, the strain state for the same section of a SF is in contrast to each other in ?{sub xx} and ?{sub yy} strain maps. The modification in the strain states was attributed to the variation in the local atomic displacements for the SF in the AlSb film on the GaAs substrate recorded in the lattice image. Finally, the single SF was found to be bounded by two 30 PDs. A pair of 30 PDs near the heteroepitaxial interface reacted to form a Lomer-Cottrell sessile dislocation located at the vertices of V-shaped SFs with opposite screw components. The roles of misfit dislocations, such as the PDs, in strain relaxation were also discussed.

  3. The discrepancies between theory and experiment in the optical emission of monolayer In(Ga)N quantum wells revisited by transmission electron microscopy

    SciTech Connect (OSTI)

    Suski, T.; Gorczyca, I.; Skrobas, K.; Schulz, T.; Albrecht, M.; Wang, X. Q.; Christensen, N. E.; Svane, A.

    2014-05-05

    Quantitative high resolution transmission electron microscopy studies of intentionally grown 1InN/nGaN short-period superlattices (SLs) were performed. The structures were found to consist of an In{sub x}Ga{sub 1−x}N monolayer with an Indium content of x = 0.33 instead of the intended x = 1. Self-consistent calculations of the band structures of 1In{sub 0.33}Ga{sub 0.67}N/nGaN SLs were carried out, including a semi-empirical correction for the band gaps. The calculated band gap, E{sub g,} as well as its pressure derivative, dE{sub g}/dp, are in very good agreement with the measured photoluminescence energy, E{sub PL}, and its pressure derivative, dE{sub PL}/dp, for a series of 1In{sub 0.33}Ga{sub 0.67}N/nGaN samples with n ranging from 2 to 40. This resolves a discrepancy found earlier between measured and calculated optical emission properties, as those calculations were made with the assumption of a 1InN/nGaN SL composition.

  4. Demonstration of an Electrochemical Liquid Cell for Operando Transmission Electron Microscopy Observation of the Lithiation/Delithiation Behavior of Si Nanowire Battery Anodes

    SciTech Connect (OSTI)

    Gu, Meng; Parent, Lucas R.; Mehdi, Beata L.; Unocic, Raymond R.; Mcdowell, Matthew T.; Sacci, Robert L.; Xu, Wu; Connell, Justin G.; Xu, Pinghong; Abellan Baeza, Patricia; Chen, Xilin; Zhang, Yaohui; Perea, Daniel E.; Evans, James E.; Lauhon, Lincoln; Zhang, Jiguang; Liu, Jun; Browning, Nigel D.; Cui, Yi; Arslan, Ilke; Wang, Chong M.

    2013-12-11

    Over the last few years, in-situ transmission electron microscopy (TEM) studies of lithium ion batteries using an open-cell configuration have helped us to gain fundamental insights into the structural and chemical evolution of the electrode materials in real time. In the standard open-cell configuration, the electrolyte is either solid lithium oxide or an ionic liquid, which is point-contacted with the electrode. This cell design is inherently different from a real battery, where liquid electrolyte forms conformal contact with electrode materials. The knowledge learnt from open cells can deviate significantly from the real battery, calling for operando TEM technique with conformal liquid electrolyte contact. In this paper, we developed an operando TEM electrochemical liquid cell to meet this need, providing the configuration of a real battery and in a relevant liquid electrolyte. To demonstrate this novel technique, we studied the lithiation/delithiation behavior of single Si nanowires. Some of lithiation/delithation behaviors of Si obtained using the liquid-cell are consistent with the results from the open-cell studies. However, we also discovered new insights different from the open cell configuration - the dynamics of the electrolyte and, potentially, a future quantitative characterization of the SEI layer formation and structural and chemical evolution.

  5. In-situ high resolution transmission electron microscopy observation of silicon nanocrystal nucleation in a SiO{sub 2} bilayered matrix

    SciTech Connect (OSTI)

    Yang, T. C.-J. Wu, L.; Lin, Z.; Jia, X.; Puthen-Veettil, B.; Zhang, T.; Conibeer, G.; Perez-Wurfl, I.; Kauffmann, Y.; Rothschild, A.

    2014-08-04

    Solid-state nucleation of Si nanocrystals in a SiO{sub 2} bilayered matrix was observed at temperatures as low as 450?C. This was achieved by aberration corrected high-resolution transmission electron microscopy (HRTEM) with real-time in-situ heating up to 600?C. This technique is a valuable characterization tool especially with the recent interest in Si nanostructures for light emitting devices, non-volatile memories, and third-generation photovoltaics which all typically require a heating step in their fabrication. The control of size, shape, and distribution of the Si nanocrystals are critical for these applications. This experimental study involves in-situ observation of the nucleation of Si nanocrystals in a SiO{sub 2} bilayered matrix fabricated through radio frequency co-sputtering. The results show that the shapes of Si nanocrystals in amorphous SiO{sub 2} bilayered matrices are irregular and not spherical, in contrast to many claims in the literature. Furthermore, the Si nanocrystals are well confined within their layers by the amorphous SiO{sub 2}. This study demonstrates the potential of in-situ HRTEM as a tool to observe the real time nucleation of Si nanocrystals in a SiO{sub 2} bilayered matrix. Furthermore, ideas for improvements on this in-situ heating HRTEM technique are discussed.

  6. Abnormal cubic-tetragonal phase transition of barium strontium titanate nanoparticles studied by in situ Raman spectroscopy and transmission electron microscopy heating experiments

    SciTech Connect (OSTI)

    Zhang, Yin; Chen, Chen; Gao, Ran; Xia, Feng; Li, YueSheng; Che, Renchao

    2015-11-02

    Phase stability of the ferroelectric materials at high temperature is extremely important to their device performance. Ba{sub x}Sr{sub 1−x}TiO{sub 3} (BST) nanoparticles with different Sr contents (x = 1, 0.91, 0.65, 0.4, and 0) are prepared by a facile hydrothermal method. Using Raman spectroscopy and transmission electron microscopy (TEM) analyses under in situ heating conditions (up to 300 °C), the phase transitions of BST nanoparticles between 25 °C and 280 °C are comprehensively investigated. The original Curie temperature of BST nanoparticles decreases abruptly with the increase in Sr content, which is more obvious than in the bulk or film material. Besides, an abnormal phase transition from cubic to tetragonal structure is observed from BST nanoparticles and the transition temperature rises along with the increase in Sr content. Direct TEM evidences including a slight lattice distortion have been provided. Differently, BaTiO{sub 3} nanoparticles remained in the tetragonal phase during the above temperature ranges.

  7. Electronic Coupling Dependence of Ultrafast Interfacial Electron...

    Office of Scientific and Technical Information (OSTI)

    Electronic Coupling Dependence of Ultrafast Interfacial Electron Transfer on Nanocrystalline Thin Films and Single Crystal Citation Details In-Document Search Title: Electronic ...

  8. In Situ Transmission Electron Microscopy

    Office of Scientific and Technical Information (OSTI)

    ... Nanofactory Atomic Force Microscopy (AFM) Stage * Measures force interactions on samples with higher sensitivity than the NanoIndentation stage * Load range between 10 - 2,000 nN * ...

  9. Transmission Workshop

    Broader source: Energy.gov [DOE]

    On November 1-2, 2012, the GTT presented a workshop on grid integration on the transmission system at the DoubleTree Crystal City near Washington, DC.

  10. Transmission Workshop

    Broader source: Energy.gov (indexed) [DOE]

    Grid Tech Team U.S. Department of Energy DOE Grid Tech Team (GTT) The Grid Tech Team ... regional diversity, AC-DC transmission and distribution solutions, ...

  11. Transmission decisions

    SciTech Connect (OSTI)

    Ellison, C.T. )

    1993-03-01

    As the US FERC moves forward to implement the transmission access provisions of the National Energy Policy Act of 1992, the debate over Regional Transmission Groups continues. Independent energy producers have much at stake in this debate and their reaction to the general RTG concept and to specific RTG proposals will weigh heavily in determining the fate of these proposals.

  12. Visible Light-Induced Electron Transfer from Di-mu-oxo Bridged Dinuclear Mn Complexes to Cr Centers in Silica Nanopores

    SciTech Connect (OSTI)

    Frei, Heinz; Weare, Walter W.; Pushkar, Yulia; Yachandra, Vittal K.; Frei, Heinz

    2008-06-03

    The compound (bpy)2MnIII(mu-O)2MnIV(bpy)2, a structural model relevant for the photosynthetic water oxidation complex, was coupled to single CrVI charge-transfer chromophores in the channels of the nanoporous oxide AlMCM-41. Mn K-edge EXAFS spectroscopy confirmed that the di-mu-oxo dinuclear Mn core of the complex is unaffected when loaded into the nanoscale pores. Observation of the 16-line EPR signal characteristic of MnIII(mu-O)2MnIV demonstrates that the majority of the loaded complexes retained their nascent oxidation state in the presence or absence of CrVI centers. The FT-Raman spectrum upon visible light excitation of the CrVI-OII --> CrV-OI ligand-to-metal charge-transfer reveals electron transfer from MnIII(mu-O)2MnIV (Mn-O stretch at 700 cm-1) to CrVI, resulting in the formation of CrV and MnIV(mu-O)2MnIV (Mn-O stretch at 645 cm-1). All initial and final states are directly observed by FT-Raman or EPR spectroscopy, and the assignments corroborated by X-ray absorption spectroscopy measurements. The endoergic charge separation products (DELTA Eo = -0.6 V) remain after several minutes, which points to spatial separation of CrV and MnIV(mu-O)2MnIV as a consequence of hole (OI) hopping as a major contributing mechanism. This is the first observation of visible light-induced oxidation of a potential water oxidation complex by a metal charge-transfer pump in a nanoporous environment. These findings will allow for the assembly and photochemical characterization of well defined transition metal molecular units, with the ultimate goal of performing endothermic, multi-electron transformations that are coupled to visible light electron pumps in nanostructured scaffolds.

  13. Rational engineering of Geobacter sulfurreducens electron transfer components: A foundation for building improved Geobacter-based bioelectrochemical technologies

    SciTech Connect (OSTI)

    Dantas, Joana M.; Morgado, Leonor; Aklujkar, Muktak; Bruix, Marta; Londer, Yuri Y.; Schiffer, Marianne; Pokkuluri, P. Raj; Salgueiro, Carlos A.

    2015-07-30

    Multiheme cytochromes have been implicated in Geobacter sulfurreducens extracellular electron transfer (EET). These proteins are potential targets to improve EET and enhance bioremediation and electrical current production by G. sulfurreducens. However, the functional characterization of multiheme cytochromes is particularly complex due to the co-existence of several microstates in solution, connecting the fully reduced and fully oxidized states. Throughout the last decade, new strategies have been developed to characterize multiheme redox proteins functionally and structurally. These strategies were used to reveal the functional mechanism of G. sulfurreducens multiheme cytochromes and also to identify key residues in these proteins for EET. In previous studies, we set the foundations for enhancement of the EET abilities of G. sulfurreducens by characterizing a family of five triheme cytochromes (PpcA-E). These periplasmic cytochromes are implicated in electron transfer between the oxidative reactions of metabolism in the cytoplasm and the reduction of extracellular terminal electron acceptors at the cell's outer surface. The results obtained suggested that PpcA can couple e-/H+ transfer, a property that might contribute to the proton electrochemical gradient across the cytoplasmic membrane for metabolic energy production. The structural and functional properties of PpcA were characterized in detail and used for rational design of a family of 23 single site PpcA mutants. In this review, we summarize the functional characterization of the native and mutant proteins. Mutants that retain the mechanistic features of PpcA and adopt preferential e-/H+ transfer pathways at lower reduction potential values compared to the wild-type protein were selected for in vivo studies as the best candidates to increase the electron transfer rate of G. sulfurreducens. For the first time G. sulfurreducens

  14. Electron-lattice interactions strongly renormalize the charge-transfer energy in the spin-chain cuprate Li2CuO2

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Johnston, Steve; Monney, Claude; Bisogni, Valentina; Zhou, Ke-Jin; Kraus, Roberto; Behr, Günter; Strocov, Vladimir N.; Málek, Jiři; Drechsler, Stefan-Ludwig; Geck, Jochen; et al

    2016-02-17

    Strongly correlated insulators are broadly divided into two classes: Mott–Hubbard insulators, where the insulating gap is driven by the Coulomb repulsion U on the transition-metal cation, and charge-transfer insulators, where the gap is driven by the charge-transfer energy Δ between the cation and the ligand anions. The relative magnitudes of U and Δ determine which class a material belongs to, and subsequently the nature of its low-energy excitations. These energy scales are typically understood through the local chemistry of the active ions. Here we show that the situation is more complex in the low-dimensional charge-transfer insulator Li2CuO2, where Δ hasmore » a large non-electronic component. Combining resonant inelastic X-ray scattering with detailed modelling, we determine how the elementary lattice, charge, spin and orbital excitations are entangled in this material. This results in a large lattice-driven renormalization of Δ, which significantly reshapes the fundamental electronic properties of Li2CuO2.« less

  15. Direct imaging of crystal structure and defects in metastable Ge{sub 2}Sb{sub 2}Te{sub 5} by quantitative aberration-corrected scanning transmission electron microscopy

    SciTech Connect (OSTI)

    Ross, Ulrich; Lotnyk, Andriy Thelander, Erik; Rauschenbach, Bernd

    2014-03-24

    Knowledge about the atomic structure and vacancy distribution in phase change materials is of foremost importance in order to understand the underlying mechanism of fast reversible phase transformation. In this Letter, by combining state-of-the-art aberration-corrected scanning transmission electron microscopy with image simulations, we are able to map the local atomic structure and composition of a textured metastable Ge{sub 2}Sb{sub 2}Te{sub 5} thin film deposited by pulsed laser deposition with excellent spatial resolution. The atomic-resolution scanning transmission electron microscopy investigations display the heterogeneous defect structure of the Ge{sub 2}Sb{sub 2}Te{sub 5} phase. The obtained results are discussed. Highly oriented Ge{sub 2}Sb{sub 2}Te{sub 5} thin films appear to be a promising approach for further atomic-resolution investigations of the phase change behavior of this material class.

  16. Light-induced electron paramagnetic resonance evidence of charge transfer in electrospun fibers containing conjugated polymer/fullerene and conjugated polymer/fullerene/carbon nanotube blends

    SciTech Connect (OSTI)

    Shames, Alexander I.; Bounioux, Celine; Katz, Eugene A.; Yerushalmi-Rozen, Rachel; Zussman, Eyal

    2012-03-12

    Electrospun sub-micron fibers containing conjugated polymer (poly(3-hexylthiophene), P3HT) with a fullerene derivative, phenyl-C61-butyric acid methylester (PCBM) or a mixture of PCBM and single-walled carbon nanotubes (SWCNTs) were studied by light-induced electron paramagnetic resonance spectroscopy. The results provide experimental evidence of electron transfer between PCBM and P3HT components in both fiber systems and suggest that the presence of a dispersing block-copolymer, which acts via physical adsorption onto the PCBM and SWCNT moieties, does not prevent electron transfer at the P3HT-PCBM interface. These findings suggest a research perspective towards utilization of fibers of functional nanocomposites in fiber-based organic optoelectronic and photovoltaic devices. The latter can be developed in the textile-type large area photovoltaics or individual fiber-based solar cells that will broaden energy applications from macro-power tools to micro-nanoscale power conversion devices and smart textiles.

  17. Photo-induced water oxidation at the aqueous GaN (1010) interface: Deprotonation kinetics of the first proton-coupled electron-transfer step

    SciTech Connect (OSTI)

    Ertem, Mehmed Z.; Kharche, Neerav; Batista, Victor S.; Hybertsen, Mark S.; Tully, John C.; Muckerman, James T.

    2015-03-12

    Photoeclectrochemical water splitting plays a key role in a promising path to the carbon-neutral generation of solar fuels. Wurzite GaN and its alloys (e.g., GaN/ZnO and InGaN) are demonstrated photocatalysts for water oxidation, and they can drive the overall water splitting reaction when coupled with co-catalysts for proton reduction. In the present work, we investigate the water oxidation mechanism on the prototypical GaN (1010) surface using a combined ab initio molecular dynamics and molecular cluster model approach taking into account the role of water dissociation and hydrogen bonding within the first solvation shell of the hydroxylated surface. The investigation of free-energy changes for the four proton-coupled electron-transfer (PCET) steps of the water oxidation mechanism shows that the first PCET step for the conversion of Ga-OH to Ga-O?? requires the highest energy input. We further examine the sequential PCETs, with the proton transfer (PT) following the electron transfer (ET), and find that photo-generated holes localize on surface NH sites is thermodynamically more favorable than OH sites. However, proton transfer from OH sites with subsequent localization of holes on oxygen atoms is kinetically favored owing to hydrogen bonding interactions at the GaN (1010)water interface. We find that the deprotonation of surface OH sites is the limiting factor for the generation of reactive oxyl radical ion intermediates and consequently for water oxidation.

  18. Photo-induced water oxidation at the aqueous GaN (101¯0) interface: Deprotonation kinetics of the first proton-coupled electron-transfer step

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Ertem, Mehmed Z.; Kharche, Neerav; Batista, Victor S.; Hybertsen, Mark S.; Tully, John C.; Muckerman, James T.

    2015-03-12

    Photoeclectrochemical water splitting plays a key role in a promising path to the carbon-neutral generation of solar fuels. Wurzite GaN and its alloys (e.g., GaN/ZnO and InGaN) are demonstrated photocatalysts for water oxidation, and they can drive the overall water splitting reaction when coupled with co-catalysts for proton reduction. In the present work, we investigate the water oxidation mechanism on the prototypical GaN (101¯0) surface using a combined ab initio molecular dynamics and molecular cluster model approach taking into account the role of water dissociation and hydrogen bonding within the first solvation shell of the hydroxylated surface. The investigation ofmore » free-energy changes for the four proton-coupled electron-transfer (PCET) steps of the water oxidation mechanism shows that the first PCET step for the conversion of –Ga-OH to –Ga-O˙⁻ requires the highest energy input. We further examine the sequential PCETs, with the proton transfer (PT) following the electron transfer (ET), and find that photo-generated holes localize on surface –NH sites is thermodynamically more favorable than –OH sites. However, proton transfer from –OH sites with subsequent localization of holes on oxygen atoms is kinetically favored owing to hydrogen bonding interactions at the GaN (101¯0)–water interface. We find that the deprotonation of surface –OH sites is the limiting factor for the generation of reactive oxyl radical ion intermediates and consequently for water oxidation.« less

  19. Evolution of titania nanotubes-supported WO{sub x} species by in situ thermo-Raman spectroscopy, X-ray diffraction and high resolution transmission electron microscopy

    SciTech Connect (OSTI)

    Cortes-Jacome, M.A.; Angeles-Chavez, C.; Morales, M.; Lopez-Salinas, E.; Toledo-Antonio, J.A.

    2007-10-15

    Structural evolution of WO{sub x} species on the surface of titania nanotubes was followed by in situ thermo-Raman spectroscopy. A total of 15 wt% of W atoms were loaded on the surface of a hydroxylated titania nanotubes by impregnation with ammonium metatungstate solution and then, the sample was thermally treated in a Linkam cell at different temperatures in nitrogen flow. The band characteristic of the W=O bond was observed at 962 cm{sup -1} in the dried sample, which vanished between 300 and 700 deg. C, and reappear again after annealing at 800 deg. C, along with a broad band centered at 935 cm{sup -1}, attributed to the v{sub 1} vibration of W=O in tetrahedral coordination. At 900 and 1000 deg. C, the broad band decomposed into four bands at 923, 934, 940 and 950 cm{sup -1}, corresponding to the symmetric and asymmetric vibration of W=O bonds in Na{sub 2}WO{sub 4} and Na{sub 2}W{sub 2}O{sub 7} phases as determined by X-ray diffraction and High resolution transmission electron microscopy (HRTEM). The structure of the nanotubular support was kept at temperatures below 450 deg. C, thereafter, it transformed into anatase being stabilized at temperatures as high as 900 deg. C. At 1000 deg. C, anatase phase partially converted into rutile. After annealing at 1000 deg. C, a core-shell model material was obtained, with a shell of ca. 5 nm thickness, composed of sodium tungstate nanoclusters, and a core composed mainly of rutile TiO{sub 2} phase. - Graphical abstract: Titania nanotubes loaded with 15 wt% W atoms were characterized from room temperature (rt) to 1000 deg. C by thermo-Raman spectroscopy in N{sub 2}. At 1000 deg. C, a core-shell model material was obtained, with a shell thickness of ca. 5 nm composed by nanoclusters of sodium tungstate, and a core composed mainly of rutile TiO{sub 2} phase.

  20. An examination of electronic file transfer between host and microcomputers for the AMPMODNET/AIMNET (Army Material Plan Modernization Network/Acquisition Information Management Network) classified network environment

    SciTech Connect (OSTI)

    Hake, K.A.

    1990-11-01

    This report presents the results of investigation and testing conducted by Oak Ridge National Laboratory (ORNL) for the Project Manager -- Acquisition Information Management (PM-AIM), and the United States Army Materiel Command Headquarters (HQ-AMC). It concerns the establishment of file transfer capabilities on the Army Materiel Plan Modernization (AMPMOD) classified computer system. The discussion provides a general context for micro-to-mainframe connectivity and focuses specifically upon two possible solutions for file transfer capabilities. The second section of this report contains a statement of the problem to be examined, a brief description of the institutional setting of the investigation, and a concise declaration of purpose. The third section lays a conceptual foundation for micro-to-mainframe connectivity and provides a more detailed description of the AMPMOD computing environment. It gives emphasis to the generalized International Business Machines, Inc. (IBM) standard of connectivity because of the predominance of this vendor in the AMPMOD computing environment. The fourth section discusses two test cases as possible solutions for file transfer. The first solution used is the IBM 3270 Control Program telecommunications and terminal emulation software. A version of this software was available on all the IBM Tempest Personal Computer 3s. The second solution used is Distributed Office Support System host electronic mail software with Personal Services/Personal Computer microcomputer e-mail software running with IBM 3270 Workstation Program for terminal emulation. Test conditions and results are presented for both test cases. The fifth section provides a summary of findings for the two possible solutions tested for AMPMOD file transfer. The report concludes with observations on current AMPMOD understanding of file transfer and includes recommendations for future consideration by the sponsor.

  1. Electron

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    density measurement by differential interferometry W. X. Ding, D. L. Brower, B. H. Deng, and T. Yates Electrical Engineering Department, University of California-Los Angeles, Los Angeles, California 90095 ͑Received 5 May 2006; presented on 10 May 2006; accepted 16 June 2006; published online 26 September 2006͒ A novel differential interferometer is being developed to measure the electron density gradient and its fluctuations. Two separate laser beams with slight spatial offset and frequency

  2. Electron

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Electron thermal transport within magnetic islands in the reversed-field pinch a... H. D. Stephens, 1,b͒ D. J. Den Hartog, 1,3 C. C. Hegna, 1,2 and J. A. Reusch 1 1 Department of Physics, University of Wisconsin-Madison, 1150 University Ave., Madison, Wisconsin 53706, USA 2 Department of Engineering Physics, University of Wisconsin-Madison, 1500 Engineering Drive, Madison, Wisconsin 53706, USA 3 Center for Magnetic Self-Organization in Laboratory and Astrophysical Plasmas, University of

  3. Theoretical analysis of the sequential proton-coupled electron transfer mechanisms for H2 oxidation and production pathways catalyzed by nickel molecular electrocatalysts

    SciTech Connect (OSTI)

    Fernandez, Laura; Horvath, Samantha; Hammes-Schiffer, Sharon

    2012-02-02

    The design of electrocatalysts for the oxidation and production of H2 is important for the development of alternative energy sources. This paper focuses on the electrocatalysts, where denotes 1,5-diaza-3,7-diphosphacyclooctane ligands with substituent groups R and R' covalently bound to the phosphorus and nitrogen atoms, respectively. Theoretical methods are used to investigate the mechanism of the step in the catalytic cycle corresponding to e ? for H2 oxidation and the reverse reaction for H2 production. This step involves electron transfer (ET) between the Ni complex and the electrode as well as proton transfer (PT) between the Ni and the N. The sequential mechanisms, PTET and ETPT, are investigated for the following (R,R) substituents: (Me,Me), (Ph,Ph), and (Ph,Bz), where Me, Ph, and Bz denote methyl, phenyl, and benzyl substituents. Density functional theory is used to calculate reduction potentials, pKas, and PT pathways, and Marcus theory is used to describe the electrochemical electron transfer, including the effects of solute and solvent reorganization energies. For the (Ph,Ph) and (Ph,Bz) systems, the sequential PTET mechanism would require surmounting a large free energy barrier for the initial PT step, followed by thermodynamically favorable or thermoneutral ET. The sequential ETPT mechanism for these systems would require a relatively large initial applied overpotential, followed by a PT reaction with a relatively low free energy barrier. Consistent with experimental data, the calculated overpotential required for the initial reduction in the ETPT mechanism is lower for the (Ph,Bz) system than for the (Ph,Ph) system. The concerted mechanism, in which the electron and proton transfer simultaneously without a stable intermediate, may be thermodynamically favorable and is a direction of future research. This material is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the

  4. Photoreactivity of ZnO nanoparticles in visible light: Effect of surface states on electron transfer reaction

    SciTech Connect (OSTI)

    Baruah, Sunandan; Dutta, Joydeep; Sinha, Sudarson Sekhar; Ghosh, Barnali; Pal, Samir Kumar; Raychaudhuri, A. K.

    2009-04-01

    Wide band gap metal oxide semiconductors such as zinc oxide (ZnO) show visible band photolysis that has been employed, among others, to degrade harmful organic contaminants into harmless mineral acids. Metal oxides show enhanced photocatalytic activity with the increase in electronic defects in the crystallites. By introducing defects into the crystal lattice of ZnO nanoparticles, we observe a redshift in the optical absorption shifting from the ultraviolet region to the visible region (400-700 nm), which is due to the creation of intermediate defect states that inhibit the electron hole recombination process. The defects were introduced by fast nucleation and growth of the nanoparticles by rapid heating using microwave irradiation and subsequent quenching during the precipitation reaction. To elucidate the nature of the photodegradation process, picosecond resolved time correlated single photon count (TCSPC) spectroscopy was carried out to record the electronic transitions resulting from the de-excitation of the electrons to their stable states. Photodegradation and TCSPC studies showed that defect engineered ZnO nanoparticles obtained through fast crystallization during growth lead to a faster initial degradation rate of methylene blue as compared to the conventionally synthesized nanoparticles.

  5. Transmission Services

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Transmission Services BPA Clarifications on the DSO216 1 Document updated on 2242015 at 3:29:25 PM B O N N E V I L L E P O W E R A D M I N I S T R A T I O N BPA Clarifications on...

  6. Transmission Planning

    Broader source: Energy.gov [DOE]

    The Department's research into a variety of tools that will improve advanced system monitoring, visualization, control, operations, and market structure will ultimately modernize the electricity transmission infrastructure to ease congestion, allow for increases in demand, and provide a greater degree of security.

  7. Quenching of electron transfer reactions through coadsorption: A study of oxygen photodesorption from TiO2(110)

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Petrik, Nikolay G.; Kimmel, Greg A.; Shen, Mingmin; Henderson, Michael A.

    2016-01-11

    Using temperature programmed desorption (TPD) and photon-stimulated desorption (PSD), we show that coadsorbates of varying binding energies on the rutile TiO2(110) surface exert a commensurate inhibiting influence on the hole-mediated photodesorption of adsorbed O2. A variety of coadsorbates (Ar, Kr, Xe, N2, CO, CO2, CH4, N2O, acetone, methanol or water) were shown to quench O2 photoactivity, with the extent correlating with the coadsorbate's gas phase basicity, which in turn determines the strength of the coadsorbate–Ti4+ bond. Coadsorbed rare gases inhibited the photodesorption of O2 by ~ 10–25%, whereas strongly bound species (water, methanol, and acetone) nearly completely inhibited O2 PSD.more » We suggest that coadsorption of these molecules inhibit the arrival probability of holes to the surface. Band-bending effects, which vary with the extent of charge transfer between the coadsorbate and the TiO2(110) surface, are not expected to be significant in the cases of the rare gases and physisorbed species. Furthermore, these results indicate that neutral coadsorbates can exert a significant influence on charge transfer events by altering the interfacial dipole in the vicinity of the target molecule.« less

  8. Numerical modeling of heat-transfer and the influence of process parameters on tailoring the grain morphology of IN718 in electron beam additive manufacturing

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Raghavan, Narendran; Dehoff, Ryan; Pannala, Sreekanth; Simunovic, Srdjan; Kirka, Michael; Turner, John; Carlson, Neil; Babu, Sudarsanam S.

    2016-04-26

    The fabrication of 3-D parts from CAD models by additive manufacturing (AM) is a disruptive technology that is transforming the metal manufacturing industry. The correlation between solidification microstructure and mechanical properties has been well understood in the casting and welding processes over the years. This paper focuses on extending these principles to additive manufacturing to understand the transient phenomena of repeated melting and solidification during electron beam powder melting process to achieve site-specific microstructure control within a fabricated component. In this paper, we have developed a novel melt scan strategy for electron beam melting of nickel-base superalloy (Inconel 718) andmore » also analyzed 3-D heat transfer conditions using a parallel numerical solidification code (Truchas) developed at Los Alamos National Laboratory. The spatial and temporal variations of temperature gradient (G) and growth velocity (R) at the liquid-solid interface of the melt pool were calculated as a function of electron beam parameters. By manipulating the relative number of voxels that lie in the columnar or equiaxed region, the crystallographic texture of the components can be controlled to an extent. The analysis of the parameters provided optimum processing conditions that will result in columnar to equiaxed transition (CET) during the solidification. Furthermore, the results from the numerical simulations were validated by experimental processing and characterization thereby proving the potential of additive manufacturing process to achieve site-specific crystallographic texture control within a fabricated component.« less

  9. Photoinduced electron transfer double fragmentation. An oxygen-mediated radical chain process in the cofragmentation of aminopinacol donors with organic halides

    SciTech Connect (OSTI)

    Chen, L.; Farahat, M.S.; Gan, H.; Whitten, D.G.; Farid, S. |

    1995-06-14

    We reprot an investigation in which excited states of amino pinacols 1-3 are reacted with the halides CCl{sub 4}, benzyl bromide, and p-cyanobenzyl bromide. Interesting results from this study include the finding that low-to-moderate quantum efficiencies for reaction are observed when the reactions are carried out under degassed conditions, indicating that the halide radical anions must survive long enough within the initial ion pair formed in the quenching step to undergo considerable return electron transfer. More strikingly we find that for certain pinacol-halide combinations reaction in aerared solutions leads to much higher efficiencies, which can be attributed to a chain reaction involving oxygen capture of a primary radical product. 25 refs., 1 fig., 1 tab.

  10. Integrated survey and design for transmission lines

    SciTech Connect (OSTI)

    Miller, M.A.; Simpson, K.D.

    1994-12-31

    Gathering and compiling information on the features and uses of the land within a proposed corridor provides the basis for selecting a route, obtaining easements, and designing and constructing a transmission line. Traditionally, gathering this information involved searches of existing maps and records to obtain the available information, which would then be supplemented with aerial photography to record current conditions. Ground surveys were performed to collect topographic data for design purposes. This information was manually transferred to drawings and other documents to show the terrain, environmentally sensitive areas, property ownership, and existing facilities. These drawing served as the base to which the transmission line right-of-way, structures, and other design information were added. As the design was completed, these drawings became the source of information for constructing the line and ultimately, the record of the facility. New technologies and the every growing need for instantly accessible information have resulted in changes in almost every step of gathering, storing and using information. Electronic data collection, global positioning systems (GPS), digitized terrain models, computerized design techniques, development of drawings using CAD, and graphical information systems (GIS) have individually resulted in significant advancements in this process. Combining these components into an integrated system, however, is truly revolutionizing transmission line engineering. This paper gives an overview of the survey and mapping information that is required for transmission line projects, review the traditional techniques that have been employed to obtain and utilize this information, and discuss the recent advances in the technology. Additionally, a system is presented that integrates the components in this process to achieve efficiency, minimize chances of errors, and provide improved access to project information.