Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Probing Sulfur Chemical and Electronic Structure with Experimental Observation and Quantitative Theoretical Prediction of Kα and Valence-to-Core Kβ X-ray Emission Spectroscopy

Abstract

An extensive experimental and theoretical study of the Kα and Kβ high-resolution X-ray emission spectroscopy (XES) of sulfur-bearing systems is presented here. This study encompasses a wide range of organic and inorganic compounds, including numerous experimental spectra from both prior published work and new measurements. Employing a linear-response time-dependent density functional theory (LR-TDDFT) approach, strong quantitative agreement is found in the calculation of energy shifts of the core-to-core Kα as well as the full range of spectral features in the valence-to-core Kβ spectrum. The ability to accurately calculate the sulfur Kα energy shift supports the use of sulfur Kα XES as a bulk-sensitive tool for assessing sulfur speciation. The fine structure of the sulfur Kβ spectrum, in conjunction with the theoretical results, is shown to be sensitive to the local electronic structure including effects of symmetry, ligand type and number, and, in the case of organosulfur compounds, to the nature of the bonded organic moiety. This agreement between theory and experiment, augmented by the potential for high-access XES measurements with the latest generation of laboratory-based spectrometers, demonstrates the possibility of broad analytical use of XES for sulfur and nearby third-row elements. The effective solution of the forward problem, i.e., successfulmore » prediction of detailed spectra from known molecular structure, also suggests future use of supervised machine learning approaches to experimental inference, as has seen recent interest for interpretation of X-ray absorption near-edge structure (XANES).« less

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Washington, Seattle, WA (United States). Dept. of Physics
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1646827
Report Number(s):
PNNL-SA-148445
Journal ID: ISSN 1089-5639
Grant/Contract Number:  
AC05-76RL01830; KC030105172685; DMR-1719797
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 124; Journal Issue: 26; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; x-rays; sulfur; oxidation state; energy; chemical calculations

Citation Formats

Holden, William M., Jahrman, Evan P., Govind, Niranjan, and Seidler, Gerald T. Probing Sulfur Chemical and Electronic Structure with Experimental Observation and Quantitative Theoretical Prediction of Kα and Valence-to-Core Kβ X-ray Emission Spectroscopy. United States: N. p., 2020. Web. doi:10.1021/acs.jpca.0c04195.
Copy to clipboard
Holden, William M., Jahrman, Evan P., Govind, Niranjan, & Seidler, Gerald T. Probing Sulfur Chemical and Electronic Structure with Experimental Observation and Quantitative Theoretical Prediction of Kα and Valence-to-Core Kβ X-ray Emission Spectroscopy. United States. https://doi.org/10.1021/acs.jpca.0c04195
Copy to clipboard
Holden, William M., Jahrman, Evan P., Govind, Niranjan, and Seidler, Gerald T. Tue . "Probing Sulfur Chemical and Electronic Structure with Experimental Observation and Quantitative Theoretical Prediction of Kα and Valence-to-Core Kβ X-ray Emission Spectroscopy". United States. https://doi.org/10.1021/acs.jpca.0c04195. https://www.osti.gov/servlets/purl/1646827.
Copy to clipboard
@article{osti_1646827,
title = {Probing Sulfur Chemical and Electronic Structure with Experimental Observation and Quantitative Theoretical Prediction of Kα and Valence-to-Core Kβ X-ray Emission Spectroscopy},
author = {Holden, William M. and Jahrman, Evan P. and Govind, Niranjan and Seidler, Gerald T},
abstractNote = {An extensive experimental and theoretical study of the Kα and Kβ high-resolution X-ray emission spectroscopy (XES) of sulfur-bearing systems is presented here. This study encompasses a wide range of organic and inorganic compounds, including numerous experimental spectra from both prior published work and new measurements. Employing a linear-response time-dependent density functional theory (LR-TDDFT) approach, strong quantitative agreement is found in the calculation of energy shifts of the core-to-core Kα as well as the full range of spectral features in the valence-to-core Kβ spectrum. The ability to accurately calculate the sulfur Kα energy shift supports the use of sulfur Kα XES as a bulk-sensitive tool for assessing sulfur speciation. The fine structure of the sulfur Kβ spectrum, in conjunction with the theoretical results, is shown to be sensitive to the local electronic structure including effects of symmetry, ligand type and number, and, in the case of organosulfur compounds, to the nature of the bonded organic moiety. This agreement between theory and experiment, augmented by the potential for high-access XES measurements with the latest generation of laboratory-based spectrometers, demonstrates the possibility of broad analytical use of XES for sulfur and nearby third-row elements. The effective solution of the forward problem, i.e., successful prediction of detailed spectra from known molecular structure, also suggests future use of supervised machine learning approaches to experimental inference, as has seen recent interest for interpretation of X-ray absorption near-edge structure (XANES).},
doi = {10.1021/acs.jpca.0c04195},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 26,
volume = 124,
place = {United States},
year = {Tue Jun 02 00:00:00 EDT 2020},
month = {Tue Jun 02 00:00:00 EDT 2020}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpca.0c04195
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 29 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Lithium-Sulfur Batteries: Progress and Prospects
journal, February 2015

  • Manthiram, Arumugam; Chung, Sheng-Heng; Zu, Chenxi
  • Advanced Materials, Vol. 27, Issue 12
  • DOI: 10.1002/adma.201405115

Rechargeable Lithium–Sulfur Batteries
journal, July 2014

  • Manthiram, Arumugam; Fu, Yongzhu; Chung, Sheng-Heng
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr500062v

Li–O2 and Li–S batteries with high energy storage
journal, January 2012

  • Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J.
  • Nature Materials, Vol. 11, Issue 1, p. 19-29
  • DOI: 10.1038/nmat3191

Iron-Sulfur Clusters: Nature's Modular, Multipurpose Structures
journal, August 1997

Interaction of Sulfur with Well-Defined Metal and Oxide Surfaces:  Unraveling the Mysteries behind Catalyst Poisoning and Desulfurization
journal, September 1999

  • Rodriguez, José A.; Hrbek, Jan
  • Accounts of Chemical Research, Vol. 32, Issue 9
  • DOI: 10.1021/ar9801191

Sulfur as a catalyst promoter or selectivity modifier in heterogeneous catalysis
journal, January 2014

  • McCue, Alan J.; Anderson, James A.
  • Catal. Sci. Technol., Vol. 4, Issue 2
  • DOI: 10.1039/C3CY00754E

Sulfur in soils
journal, May 2009

  • Wilhelm Scherer, Heinrich
  • Journal of Plant Nutrition and Soil Science, Vol. 172, Issue 3
  • DOI: 10.1002/jpln.200900037

Global and regional trends of atmospheric sulfur
journal, January 2019

X-ray Emission Spectroscopy Evidences a Central Carbon in the Nitrogenase Iron-Molybdenum Cofactor
journal, November 2011

Valence-to-Core X-ray Emission Spectroscopy: A Sensitive Probe of the Nature of a Bound Ligand
journal, April 2011

  • Pollock, Christopher J.; DeBeer, Serena
  • Journal of the American Chemical Society, Vol. 133, Issue 14
  • DOI: 10.1021/ja200560z

Probing Valence Orbital Composition with Iron Kβ X-ray Emission Spectroscopy
journal, July 2010

  • Lee, Nicole; Petrenko, Taras; Bergmann, Uwe
  • Journal of the American Chemical Society, Vol. 132, Issue 28
  • DOI: 10.1021/ja101281e

Insights into the Geometric and Electronic Structure of Transition Metal Centers from Valence-to-Core X-ray Emission Spectroscopy
journal, September 2015

Valence to Core X-ray Emission Spectroscopy
journal, May 2014

Sulfur-Metal Orbital Hybridization in Sulfur-Bearing Compounds Studied by X-ray Emission Spectroscopy
journal, July 2010

  • Mori, R. Alonso; Paris, E.; Giuli, G.
  • Inorganic Chemistry, Vol. 49, Issue 14
  • DOI: 10.1021/ic100304z

Electronic Structure of Third-Row Elements in Different Local Symmetries Studied by Valence-to-Core X-ray Emission Spectroscopy
journal, May 2016

Chemical effects in X-ray Kα and Kβ emission spectra of sulfur in organic compounds
journal, January 1979

A Modern Laboratory XAFS Cookbook
journal, May 2016

A laboratory-based hard x-ray monochromator for high-resolution x-ray emission spectroscopy and x-ray absorption near edge structure measurements
journal, November 2014

  • Seidler, G. T.; Mortensen, D. R.; Remesnik, A. J.
  • Review of Scientific Instruments, Vol. 85, Issue 11
  • DOI: 10.1063/1.4901599

Benchtop Nonresonant X-ray Emission Spectroscopy: Coming Soon to Laboratories and XAS Beamlines Near You?
journal, May 2016

A compact dispersive refocusing Rowland circle X-ray emission spectrometer for laboratory, synchrotron, and XFEL applications
journal, July 2017

  • Holden, William M.; Hoidn, Oliver R.; Ditter, Alexander S.
  • Review of Scientific Instruments, Vol. 88, Issue 7
  • DOI: 10.1063/1.4994739

An improved laboratory-based x-ray absorption fine structure and x-ray emission spectrometer for analytical applications in materials chemistry research
journal, February 2019

  • Jahrman, Evan P.; Holden, William M.; Ditter, Alexander S.
  • Review of Scientific Instruments, Vol. 90, Issue 2
  • DOI: 10.1063/1.5049383

A novel von Hamos spectrometer for efficient X-ray emission spectroscopy in the laboratory
journal, May 2014

  • Anklamm, Lars; Schlesiger, Christopher; Malzer, Wolfgang
  • Review of Scientific Instruments, Vol. 85, Issue 5
  • DOI: 10.1063/1.4875986

Laboratory-scale X-ray absorption spectroscopy approach for actinide research: Experiment at the uranium L3-edge
journal, August 2018

Laboratory-based micro-X-ray fluorescence setup using a von Hamos crystal spectrometer and a focused beam X-ray tube
journal, April 2014

  • Kayser, Y.; Błachucki, W.; Dousse, J. -Cl.
  • Review of Scientific Instruments, Vol. 85, Issue 4
  • DOI: 10.1063/1.4869340

Laboratory von Hámos X-ray spectroscopy for routine sample characterization
journal, October 2016

  • Németh, Zoltán; Szlachetko, Jakub; Bajnóczi, Éva G.
  • Review of Scientific Instruments, Vol. 87, Issue 10
  • DOI: 10.1063/1.4964098

High-resolution Laue-type DuMond curved crystal spectrometer
journal, September 2013

  • Szlachetko, M.; Berset, M.; Dousse, J. -Cl.
  • Review of Scientific Instruments, Vol. 84, Issue 9
  • DOI: 10.1063/1.4821621

Johann-type laboratory-scale x-ray absorption spectrometer with versatile detection modes
journal, March 2019

  • Honkanen, Ari-Pekka; Ollikkala, Sami; Ahopelto, Taru
  • Review of Scientific Instruments, Vol. 90, Issue 3
  • DOI: 10.1063/1.5084049

In-house setup for laboratory-based x-ray absorption fine structure spectroscopy measurements
journal, July 2019

  • Zeeshan, F.; Hoszowska, J.; Loperetti-Tornay, L.
  • Review of Scientific Instruments, Vol. 90, Issue 7
  • DOI: 10.1063/1.5094873

A laboratory-based double X-ray spectrometer for simultaneous X-ray emission and X-ray absorption studies
journal, January 2019

  • Błachucki, Wojciech; Czapla-Masztafiak, Joanna; Sá, Jacinto
  • Journal of Analytical Atomic Spectrometry, Vol. 34, Issue 7
  • DOI: 10.1039/C9JA00159J

A laboratory spectrometer for high throughput X-ray emission spectroscopy in catalysis research
journal, November 2018

  • Malzer, Wolfgang; Grötzsch, Daniel; Gnewkow, Richard
  • Review of Scientific Instruments, Vol. 89, Issue 11
  • DOI: 10.1063/1.5035171

Variable Rowland radius laboratory vacuum surface-sensitive x-ray absorption fine structure spectrometer
journal, February 2007

  • Yuryev, Yu. N.; Lee, Hwack-Joo; Park, Hyun-Min
  • Review of Scientific Instruments, Vol. 78, Issue 2
  • DOI: 10.1063/1.2669591

Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy
journal, May 2018

  • Holden, William M.; Seidler, Gerald T.; Cheah, Singfoong
  • The Journal of Physical Chemistry A, Vol. 122, Issue 23
  • DOI: 10.1021/acs.jpca.8b02816

Determination of Hexavalent Chromium Fractions in Plastics Using Laboratory-Based, High-Resolution X-ray Emission Spectroscopy
journal, April 2018

Probing Surface Defects of InP Quantum Dots Using Phosphorus Kα and Kβ X-ray Emission Spectroscopy
journal, August 2018

4-1: Invited Paper: Role of Phosphorus Oxidation in Controlling the Luminescent Properties of Indium Phosphide Quantum Dots
journal, May 2018

  • Cossairt, Brandi M.; Stein, Jennifer L.; Holden, William M.
  • SID Symposium Digest of Technical Papers, Vol. 49, Issue 1
  • DOI: 10.1002/sdtp.12481

Classification of local chemical environments from x-ray absorption spectra using supervised machine learning
journal, March 2019

Supervised Machine-Learning-Based Determination of Three-Dimensional Structure of Metallic Nanoparticles
journal, October 2017

  • Timoshenko, Janis; Lu, Deyu; Lin, Yuewei
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 20
  • DOI: 10.1021/acs.jpclett.7b02364

An X-Ray Emission Spectroscopic Investigation of the Chemical Bond of Sulfur. I. The Peak Shift of K α and the Number of Valence Electrons of the Sulfur Atom in Compounds
journal, February 1967

  • Sato, Toshio; Takahashi, Yoshihito; Yabe, Katsumasa
  • Bulletin of the Chemical Society of Japan, Vol. 40, Issue 2
  • DOI: 10.1246/bcsj.40.298

An X-Ray Emission Spectroscopic Investigation of the Chemical Bond of Sulfur. II. The Number of Valence Electrons of the Sulfur Atom in Organic Compounds
journal, September 1969

  • Takahashi, Yoshihito; Yabe, Katsumasa; Sato, Toshio
  • Bulletin of the Chemical Society of Japan, Vol. 42, Issue 9
  • DOI: 10.1246/bcsj.42.2707

Possibility of sulphur-oxygen substitution in YBa2Cu3O6+xSy analyzed by means of X-ray emission spectroscopy
journal, October 1993

  • Yarmoshenko, Yu. M.; Trofimova, V. A.; Elokhina, L. V.
  • Journal of Physics and Chemistry of Solids, Vol. 54, Issue 10
  • DOI: 10.1016/0022-3697(93)90169-R

X-ray emission spectra and valence state of sulphur atoms of YBa 2 ((CuO) 1-x (NiS) x ) 3 O 4- delta
journal, January 1995

  • Yarmoshenko, Yu M.; Trofimova, V. A.; Dolgih, V. E.
  • Journal of Physics: Condensed Matter, Vol. 7, Issue 1
  • DOI: 10.1088/0953-8984/7/1/018

X-ray determination of effective charges on sulphur, phosphorus, silicon and chlorine atoms
journal, January 1993

Electronic Structure of Sulfur Studied by X-ray Absorption and Emission Spectroscopy
journal, August 2009

  • Alonso Mori, R.; Paris, E.; Giuli, G.
  • Analytical Chemistry, Vol. 81, Issue 15
  • DOI: 10.1021/ac900970z

Sulfur K-edge XANES Spectroscopy as a Tool for Understanding Sulfur Dynamics in Soil Organic Matter
journal, November 2003

  • Solomon, Dawit; Lehmann, Johannes; Martínez, Carmen Enid
  • Soil Science Society of America Journal, Vol. 67, Issue 6
  • DOI: 10.2136/sssaj2003.1721

Quantitative analysis of all major forms of sulfur in coal by x-ray absorption fine structure spectroscopy
journal, July 1991

  • Huffman, G. P.; Mitra, S.; Huggins, F. E.
  • Energy & Fuels, Vol. 5, Issue 4
  • DOI: 10.1021/ef00028a008

Sulfur K-edge XANES analysis of natural and synthetic basaltic glasses: Implications for S speciation and S content as function of oxygen fugacity
journal, October 2010

  • Jugo, Pedro J.; Wilke, Max; Botcharnikov, Roman E.
  • Geochimica et Cosmochimica Acta, Vol. 74, Issue 20
  • DOI: 10.1016/j.gca.2010.07.022

Direct determination and quantification of sulfur forms in coals from the Argonne Premium Sample Program
journal, January 1991

  • George, Graham N.; Gorbaty, Martin L.; Kelemen, Simon R.
  • Energy & Fuels, Vol. 5, Issue 1
  • DOI: 10.1021/ef00025a016

Sulfur Speciation in Soil by S K -Edge XANES Spectroscopy: Comparison of Spectral Deconvolution and Linear Combination Fitting
journal, April 2011

  • Prietzel, Jörg; Botzaki, Anna; Tyufekchieva, Nora
  • Environmental Science & Technology, Vol. 45, Issue 7
  • DOI: 10.1021/es102180a

XANES calibrations for the oxidation state of iron in a silicate glass
journal, July 2003

  • Berry, Andrew J.; O’Neill, Hugh St. C.; Jayasuriya, Kasthuri D.
  • American Mineralogist, Vol. 88, Issue 7
  • DOI: 10.2138/am-2003-0704

The Interpretation of Sulfur K-Edge XANES Spectra: A Case Study on Thiophenic and Aliphatic Sulfur Compounds
journal, March 2009

  • Mijovilovich, A.; Pettersson, L. G. M.; Mangold, S.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 12
  • DOI: 10.1021/jp806823c

Description of the Ground-State Covalencies of the Bis(dithiolato) Transition-Metal Complexes from X-ray Absorption Spectroscopy and Time-Dependent Density-Functional Calculations
journal, March 2007

  • Ray, Kallol; DeBeer George, Serena; Solomon, Edward I.
  • Chemistry - A European Journal, Vol. 13, Issue 10
  • DOI: 10.1002/chem.200601425

Dithiolene radicals: Sulfur K-edge X-ray absorption spectroscopy and Harry's intuition
journal, April 2011

An X-Ray Emission Spectroscopic Investigation of the Chemical Bond of Sulfur. III. The Profile of S K β Band in Sulfur Compounds
journal, November 1969

  • Takahashi, Yoshihito; Yabe, Katsumasa
  • Bulletin of the Chemical Society of Japan, Vol. 42, Issue 11
  • DOI: 10.1246/bcsj.42.3064

X-ray emission spectra of YSr2Cu3O7−δ containing sulphate and phosphate groups
journal, May 1994

Electronic structure of cuprates containing sulfur and phosphorus oxyanions
journal, October 1995

Sulfur K β x-ray emission spectra and electronic structures of some metal sulfides
journal, July 1974

Sulfur K β X-Ray Emission Bands and Valence-Band Structures of Transition-Metal Disulfides
journal, June 1976

  • Sugiura, Chikara; Suzuki, Isao; Kashiwakura, Jiro
  • Journal of the Physical Society of Japan, Vol. 40, Issue 6
  • DOI: 10.1143/JPSJ.40.1720

Kβ X-Ray Emission and K X-Ray Absorption Spectra of Sulfur in Sulfate Compounds
journal, August 1993

  • Sugiura, Chikara
  • Japanese Journal of Applied Physics, Vol. 32, Issue Part 1, No. 8
  • DOI: 10.1143/JJAP.32.3509

K β X-Ray Emission Spectra and Chemical Environments of Phosphorus and Sulfur in Various Compounds
journal, October 1995

  • Sugiura, Chikara
  • Journal of the Physical Society of Japan, Vol. 64, Issue 10
  • DOI: 10.1143/JPSJ.64.3840

Sulfur K β X-Ray Emission Spectra and Valence-Band Structures of Metal Sulfides
journal, February 1997

  • Sugiura, Chikara; Yorikawa, Hiroharu; Muramatsu, Shinji
  • Journal of the Physical Society of Japan, Vol. 66, Issue 2
  • DOI: 10.1143/JPSJ.66.503

Design of a Double-Crystal X-Ray Vacuum Spectrometer
journal, September 1932

A wide-range, single-axis, vacuum two-crystal spectrometer for fluorescent X-ray analysis
journal, March 1972

  • Gohshi, Yohichi; Hukao, Yoshiro; Hori, Kohei
  • Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 27, Issue 3
  • DOI: 10.1016/0584-8547(72)80016-8

Simple quasi‐two‐crystal x‐ray spectrometer
journal, May 1983

  • Taniguchi, Kazuo
  • Review of Scientific Instruments, Vol. 54, Issue 5
  • DOI: 10.1063/1.1137437

Molecular-Orbital Interpretation of the X-Ray K Spectra from α-Sulfur
journal, June 1971

  • Sugiura, Chikara
  • Journal of the Physical Society of Japan, Vol. 30, Issue 6
  • DOI: 10.1143/JPSJ.30.1766

Molecular Orbital Interpretation of X-Ray Emission Spectra II. Sulfur and chlorine Kβ spectra of some inorganic anions
journal, September 1971

Discrete Variational Xα Cluster Calculations. IV. Application to X-Ray Emission Study
journal, November 1980

  • Adachi, Hirohiko; Taniguchi, Kazuo
  • Journal of the Physical Society of Japan, Vol. 49, Issue 5
  • DOI: 10.1143/JPSJ.49.1944

Calculation of sulfur K ß X-ray spectra
journal, April 1993

  • Eiichirou, Uda; Jun, Kawai; Uda, M.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 75, Issue 1-4
  • DOI: 10.1016/0168-583X(93)95604-4

Intensity analysis of S Kß emission spectra of Na2SO3 by the use of DV-Xα MO method
journal, April 1993

  • Mogi, M.; Ota, A.; Ebihara, S.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 75, Issue 1-4
  • DOI: 10.1016/0168-583X(93)95603-3

Chemical speciation via X-ray emission spectroscopy in the tender X-ray range
journal, January 2016

  • Petric, Marko; Kavčič, Matjaž
  • Journal of Analytical Atomic Spectrometry, Vol. 31, Issue 2
  • DOI: 10.1039/C5JA00394F

Quantum Chemical Calculations of X-ray Emission Spectroscopy
journal, September 2014

  • Wadey, Jack D.; Besley, Nicholas A.
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 10
  • DOI: 10.1021/ct500566k

Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory
journal, November 2015

  • Zhang, Yu; Mukamel, Shaul; Khalil, Munira
  • Journal of Chemical Theory and Computation, Vol. 11, Issue 12
  • DOI: 10.1021/acs.jctc.5b00763

Valence‐to‐Core X‐ray Emission Spectroscopy as a Probe of O−O Bond Activation in Cu 2 O 2 Complexes
journal, July 2019

  • Cutsail, George E.; Gagnon, Nicole L.; Spaeth, Andrew D.
  • Angewandte Chemie International Edition, Vol. 58, Issue 27
  • DOI: 10.1002/anie.201903749

Valence‐to‐core X‐ray emission spectroscopy of Ti, TiO, and TiO 2 by means of a double full‐cylinder crystal von Hamos spectrometer
journal, December 2018

  • Wansleben, Malte; Vinson, John; Holfelder, Ina
  • X-Ray Spectrometry, Vol. 48, Issue 2
  • DOI: 10.1002/xrs.3000

Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy
journal, January 2017

  • March, Anne Marie; Assefa, Tadesse A.; Boemer, Christina
  • The Journal of Physical Chemistry C, Vol. 121, Issue 5
  • DOI: 10.1021/acs.jpcc.6b12940

A Restricted Open Configuration Interaction with Singles Method To Calculate Valence-to-Core Resonant X-ray Emission Spectra: A Case Study
journal, September 2017

In search of metal hydrides: an X-ray absorption and emission study of [NiFe] hydrogenase model complexes
journal, January 2016

  • Hugenbruch, Stefan; Shafaat, Hannah S.; Krämer, Tobias
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 16
  • DOI: 10.1039/C5CP07293J

Manganese Kβ X-ray Emission Spectroscopy As a Probe of Metal–Ligand Interactions
journal, September 2011

  • Beckwith, Martha A.; Roemelt, Michael; Collomb, Marie-Noëlle
  • Inorganic Chemistry, Vol. 50, Issue 17
  • DOI: 10.1021/ic200970t

Ligand-Sensitive But Not Ligand-Diagnostic: Evaluating Cr Valence-to-Core X-ray Emission Spectroscopy as a Probe of Inner-Sphere Coordination
journal, December 2014

  • MacMillan, Samantha N.; Walroth, Richard C.; Perry, Demetra M.
  • Inorganic Chemistry, Vol. 54, Issue 1
  • DOI: 10.1021/ic502152r

Study of Iron Dimers Reveals Angular Dependence of Valence-to-Core X-ray Emission Spectra
journal, September 2014

  • Pollock, Christopher J.; Lancaster, Kyle M.; Finkelstein, Kenneth D.
  • Inorganic Chemistry, Vol. 53, Issue 19
  • DOI: 10.1021/ic501462y

HERFD-XAS and valence-to-core-XES: new tools to push the limits in research with hard X-rays?
journal, January 2014

Valence-to-Core X-Ray Emission Spectroscopy of Iron-Carbonyl Complexes: Implications for the Examination of Catalytic Intermediates
journal, October 2013

  • Delgado-Jaime, Mario Ulises; DeBeer , Serena; Bauer, Matthias
  • Chemistry - A European Journal, Vol. 19, Issue 47
  • DOI: 10.1002/chem.201301913

Ligand Identification in Titanium Complexes Using X-ray Valence-to-Core Emission Spectroscopy
journal, September 2010

  • Swarbrick, Janine C.; Kvashnin, Yaroslav; Schulte, Karina
  • Inorganic Chemistry, Vol. 49, Issue 18
  • DOI: 10.1021/ic100755t

X-ray Emission Spectroscopy To Study Ligand Valence Orbitals in Mn Coordination Complexes
journal, September 2009

  • Smolentsev, Grigory; Soldatov, Alexander V.; Messinger, Johannes
  • Journal of the American Chemical Society, Vol. 131, Issue 36
  • DOI: 10.1021/ja808526m

Anisotropic valence→core x-ray fluorescence from a [Rh(en)3][Mn(N)(CN)5]⋅H2O single crystal: Experimental results and density functional calculations
journal, February 2002

  • Bergmann, U.; Bendix, J.; Glatzel, P.
  • The Journal of Chemical Physics, Vol. 116, Issue 5
  • DOI: 10.1063/1.1419062

On the sensitivity of hard X-ray spectroscopies to the chemical state of Br
journal, January 2013

  • Bordage, Amélie; Pápai, Mátyás; Sas, Norbert S.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 26
  • DOI: 10.1039/c3cp50367d

The X-Ray Emission Spectra of the Compounds of Third-period Elements. VI. The Relationship between the K α and K β Spectra
journal, July 1973

  • Takahashi, Yoshihito
  • Bulletin of the Chemical Society of Japan, Vol. 46, Issue 7
  • DOI: 10.1246/bcsj.46.2039

Chemical State Analysis of Phosphorus Performed by X-ray Emission Spectroscopy
journal, May 2015

Chemical-state Analysis by Means of Soft X-Ray Spectroscopy. II. K β Spectra for Phosphorus, Sulfur, and Chlorine in Various Compounds
journal, April 1984

  • Taniguchi, Kazuo
  • Bulletin of the Chemical Society of Japan, Vol. 57, Issue 4
  • DOI: 10.1246/bcsj.57.915

A color x-ray camera for 2–6 keV using a mass produced back illuminated complementary metal oxide semiconductor sensor
journal, September 2018

  • Holden, William M.; Hoidn, Oliver R.; Seidler, Gerald T.
  • Review of Scientific Instruments, Vol. 89, Issue 9
  • DOI: 10.1063/1.5047934

Time-Dependent Density Functional Response Theory for Molecules
book, November 1995

An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules
journal, November 1998

  • Stratmann, R. Eric; Scuseria, Gustavo E.; Frisch, Michael J.
  • The Journal of Chemical Physics, Vol. 109, Issue 19
  • DOI: 10.1063/1.477483

Time-dependent density functional theory for radicals
journal, March 1999

Calibration of Scalar Relativistic Density Functional Theory for the Calculation of Sulfur K-Edge X-ray Absorption Spectra
journal, February 2010

  • DeBeer George, Serena; Neese, Frank
  • Inorganic Chemistry, Vol. 49, Issue 4
  • DOI: 10.1021/ic902202s

Molecular structure and stability of dissolved lithium polysulfide species
journal, January 2014

  • Vijayakumar, M.; Govind, Niranjan; Walter, Eric
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 22
  • DOI: 10.1039/C4CP00889H

Structure and Dynamics of Polysulfide Clusters in a Nonaqueous Solvent Mixture of 1,3-Dioxolane and 1,2-Dimethoxyethane
journal, February 2019

Time-dependent density functional calculations of ligand K-edge X-ray absorption spectra
journal, March 2008

  • DeBeer George, Serena; Petrenko, Taras; Neese, Frank
  • Inorganica Chimica Acta, Vol. 361, Issue 4
  • DOI: 10.1016/j.ica.2007.05.046

Prediction of Iron K-Edge Absorption Spectra Using Time-Dependent Density Functional Theory †
journal, December 2008

  • DeBeer George, Serena; Petrenko, Taras; Neese, Frank
  • The Journal of Physical Chemistry A, Vol. 112, Issue 50
  • DOI: 10.1021/jp803174m

Time-Dependent Density Functional Theory Study of the X-ray Absorption Spectroscopy of Acetylene, Ethylene, and Benzene on Si(100)
journal, January 2007

  • Besley, Nicholas A.; Noble, Adam
  • The Journal of Physical Chemistry C, Vol. 111, Issue 8
  • DOI: 10.1021/jp065160x

Linear-Response and Real-Time Time-Dependent Density Functional Theory Studies of Core-Level Near-Edge X-Ray Absorption
journal, August 2012

  • Lopata, K.; Van Kuiken, B. E.; Khalil, M.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 9
  • DOI: 10.1021/ct3005613

Quantitatively Probing the Al Distribution in Zeolites
journal, May 2014

  • Vjunov, Aleksei; Fulton, John L.; Huthwelker, Thomas
  • Journal of the American Chemical Society, Vol. 136, Issue 23
  • DOI: 10.1021/ja501361v

Core and valence excitations in resonant X-ray spectroscopy using restricted excitation window time-dependent density functional theory
journal, November 2012

  • Zhang, Yu; Biggs, Jason D.; Healion, Daniel
  • The Journal of Chemical Physics, Vol. 137, Issue 19
  • DOI: 10.1063/1.4766356

Simulating Ru L 3 -Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers
journal, May 2013

  • Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 21
  • DOI: 10.1021/jp401020j

Tracking the Chemical Transformations at the Brønsted Acid Site upon Water-Induced Deprotonation in a Zeolite Pore
journal, October 2017

Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths
journal, April 2018

  • Ross, Matthew; Andersen, Amity; Fox, Zachary W.
  • The Journal of Physical Chemistry B, Vol. 122, Issue 19
  • DOI: 10.1021/acs.jpcb.7b12532

Unraveling the spectral signatures of solvent ordering in K-edge XANES of aqueous Na +
journal, September 2018

  • Galib, M.; Schenter, G. K.; Mundy, C. J.
  • The Journal of Chemical Physics, Vol. 149, Issue 12
  • DOI: 10.1063/1.5024568

Revisiting the hydration structure of aqueous Na +
journal, February 2017

  • Galib, M.; Baer, M. D.; Skinner, L. B.
  • The Journal of Chemical Physics, Vol. 146, Issue 8
  • DOI: 10.1063/1.4975608

Supersaturated calcium carbonate solutions are classical
journal, January 2018

  • Henzler, Katja; Fetisov, Evgenii O.; Galib, Mirza
  • Science Advances, Vol. 4, Issue 1
  • DOI: 10.1126/sciadv.aao6283

Time-dependent density functional theory within the Tamm–Dancoff approximation
journal, December 1999

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

Maximum Overlap Atomic and Molecular Orbitals
journal, July 1961

  • Lykos, Peter G.; Schmeising, Howard N.
  • The Journal of Chemical Physics, Vol. 35, Issue 1
  • DOI: 10.1063/1.1731901

Corresponding Orbitals and the Nonorthogonality Problem in Molecular Quantum Mechanics
journal, September 1967

  • King, Harry F.; Stanton, Richard E.; Kim, Hojing
  • The Journal of Chemical Physics, Vol. 47, Issue 6
  • DOI: 10.1063/1.1712221

Chemical-effect variation of Kβ/Kα X-ray intensity ratios in 3d elements
journal, August 2002

PubChem 2019 update: improved access to chemical data
journal, October 2018

  • Kim, Sunghwan; Chen, Jie; Cheng, Tiejun
  • Nucleic Acids Research, Vol. 47, Issue D1
  • DOI: 10.1093/nar/gky1033

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements
journal, October 1982

  • Francl, Michelle M.; Pietro, William J.; Hehre, Warren J.
  • The Journal of Chemical Physics, Vol. 77, Issue 7, p. 3654-3665
  • DOI: 10.1063/1.444267

Self-consistent molecular-orbital methods. 22. Small split-valence basis sets for second-row elements
journal, May 1982

  • Gordon, Mark S.; Binkley, J. Stephen; Pople, John A.
  • Journal of the American Chemical Society, Vol. 104, Issue 10
  • DOI: 10.1021/ja00374a017

The influence of polarization functions on molecular orbital hydrogenation energies
journal, January 1973

  • Hariharan, P. C.; Pople, J. A.
  • Theoretica Chimica Acta, Vol. 28, Issue 3
  • DOI: 10.1007/BF00533485

Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
journal, March 1972

  • Hehre, W. J.; Ditchfield, R.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261
  • DOI: 10.1063/1.1677527

Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
journal, January 1980

  • Krishnan, R.; Binkley, J. S.; Seeger, R.
  • The Journal of Chemical Physics, Vol. 72, Issue 1
  • DOI: 10.1063/1.438955

Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18
journal, May 1980

  • McLean, A. D.; Chandler, G. S.
  • The Journal of Chemical Physics, Vol. 72, Issue 10, p. 5639-5648
  • DOI: 10.1063/1.438980

Segmented contracted basis sets for atoms H through Xe: Sapporo-(DK)-nZP sets (n = D, T, Q)
journal, February 2012

  • Noro, Takeshi; Sekiya, Masahiro; Koga, Toshikatsu
  • Theoretical Chemistry Accounts, Vol. 131, Issue 2
  • DOI: 10.1007/s00214-012-1124-z

Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999

  • Adamo, Carlo; Barone, Vincenzo
  • The Journal of Chemical Physics, Vol. 110, Issue 13
  • DOI: 10.1063/1.478522

Refinement of the crystal structures of realgar, AsS and orpiment, As 2 S 3 *
journal, October 1972

First-principles thousand-atom quantum dot calculations
journal, April 2004

Visible Light Absorption of N-Doped TiO 2 Rutile Using (LR/RT)-TDDFT and Active Space EOMCCSD Calculations
journal, October 2011

  • Govind, N.; Lopata, K.; Rousseau, R.
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 21
  • DOI: 10.1021/jz201118r

Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi
journal, January 1985

  • Wadt, Willard R.; Hay, P. Jeffrey
  • The Journal of Chemical Physics, Vol. 82, Issue 1
  • DOI: 10.1063/1.448800

Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals
journal, January 1985

  • Hay, P. Jeffrey; Wadt, Willard R.
  • The Journal of Chemical Physics, Vol. 82, Issue 1, p. 299-310
  • DOI: 10.1063/1.448975

Energy‐adjusted a b i n i t i o pseudopotentials for the first row transition elements
journal, January 1987

  • Dolg, M.; Wedig, U.; Stoll, H.
  • The Journal of Chemical Physics, Vol. 86, Issue 2
  • DOI: 10.1063/1.452288

Correlation consistent valence basis sets for use with the Stuttgart–Dresden–Bonn relativistic effective core potentials: The atoms Ga–Kr and In–Xe
journal, February 2001

  • Martin, Jan M. L.; Sundermann, Andreas
  • The Journal of Chemical Physics, Vol. 114, Issue 8
  • DOI: 10.1063/1.1337864

Ab initio energy-adjusted pseudopotentials for elements of groups 13–17
journal, December 1993

X-ray transition energies: new approach to a comprehensive evaluation
journal, January 2003

  • Deslattes, Richard D.; Kessler, Ernest G.; Indelicato, P.
  • Reviews of Modern Physics, Vol. 75, Issue 1
  • DOI: 10.1103/RevModPhys.75.35

The anisotropy of X-ray emission spectra for 2H-MoS2 single crystals
journal, January 1983

  • Yarmoshenko, Yu. M.; Cherkashenko, V. M.; Kurmaev, E. Z.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 32, Issue 2
  • DOI: 10.1016/0368-2048(83)85088-9

Polarized X-Ray Emission Spectra of Single Crystals
journal, July 1984

Electronic structure of black phosphorus studied by polarized soft-x-ray emission and absorption spectroscopy
journal, August 1984

Partial densities of states with polarized oxygen Kα X-ray emission of YBa2Cu3O7−δ
journal, July 1991

Polarized x-ray emission studies of methyl chloride and the chlorofluoromethanes
journal, March 1991

High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information
journal, January 2005

Polarized x-ray-absorption spectroscopy of the uranyl ion: Comparison of experiment and theory
journal, July 1996

Role of inversion symmetry and multipole effects in nonresonant x-ray Raman scattering from icosahedral B 4 C
journal, March 2004

The electronic transitions of dibenzothiophene: linear dichroism spectroscopy and quantum chemical calculations
journal, December 2003

Electronic transitions of fluorene, dibenzofuran, carbazole, and dibenzothiophene: From the onset of absorption to the ionization threshold
journal, November 2010

  • Nguyen, Duy Duc; Trunk, John; Nakhimovsky, Lina
  • Journal of Molecular Spectroscopy, Vol. 264, Issue 1
  • DOI: 10.1016/j.jms.2010.08.009
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: