Electronically Nonadiabatic Structural Transformations Promoted by Electron Beams

Lingerfelt, David B.; Ganesh, Panchapakesan; Jakowski, Jacek; Sumpter, Bobby G.

doi:10.1002/adfm.201901901

Title: Electronically Nonadiabatic Structural Transformations Promoted by Electron Beams

Journal Article · 07 June 2019 · Advanced Functional Materials

DOI: https://doi.org/10.1002/adfm.201901901 · OSTI ID:1524863

^[1];

^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Abstract The use of scanning transmission electron microscopes to manipulate substitutional defects in graphene has recently been demonstrated and modeled using ground state molecular dynamics, but the role of electronic excitations induced through inelastic electron scattering in promoting these transformations has so‐far remained unexplored. Here, probed are the effects of electronic excitation on the structural dynamics of graphene quantum dots of differing edge morphologies that are substitutionally doped with silicon or phosphorous. The ground and excited state potential energy barriers for pyramidal inversion of these nonplanar doped species are evaluated using time‐dependent density functional theory. Optically bright excited states in which the barrier is decreased are identified in the low energy region of the electronic spectrum, suggesting that photoexcitation can modulate the reactivity of defects in graphene under electron beam irradiation. Coupling matrix elements between these inversion‐favoring excited states and the ground state and time‐domain simulations of the material's response to a point charge impulse indicate that focusing an electron beam near the defect can also lead to population of these states, suggesting that beam electrons incident on a defect can both excite the material to an inversion‐favoring state and transfer momentum to the defect to initiate the inversion.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; USDOE

Grant/Contract Number:: AC05-00OR22725; DE‐AC05‐00OR22725

OSTI ID:: 1524863

Alternate ID(s):: OSTI ID: 1525534

Journal Information:: Advanced Functional Materials, Vol. TBD, Issue N/A; ISSN 1616-301X

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (65)

Molecular Single-Bond Covalent Radii for Elements 1-118 Pyykkö, Pekka; Atsumi, Michiko Chemistry - A European Journal, Vol. 15, Issue 1 https://doi.org/10.1002/chem.200800987	journal	January 2009
Building Structures Atom by Atom via Electron Beam Manipulation Dyck, Ondrej; Kim, Songkil; Jimenez-Izal, Elisa Small, Vol. 14, Issue 38 https://doi.org/10.1002/smll.201801771	journal	August 2018
Heteroatom-doped graphene materials: syntheses, properties and applications Wang, Xuewan; Sun, Gengzhi; Routh, Parimal Chem. Soc. Rev., Vol. 43, Issue 20 https://doi.org/10.1039/C4CS00141A	journal	January 2014
Unconventional superconductivity in magic-angle graphene superlattices Cao, Yuan; Fatemi, Valla; Fang, Shiang Nature, Vol. 556, Issue 7699 https://doi.org/10.1038/nature26160	journal	March 2018
Entanglement, excitations, and correlation effects in narrow zigzag graphene nanoribbons Hagymási, I.; Legeza, Ö. Physical Review B, Vol. 94, Issue 16 https://doi.org/10.1103/PhysRevB.94.165147	journal	October 2016
Spin-spin and spin-orbit interactions in nanographene fragments: A quantum chemistry approach Perumal, S.; Minaev, B.; Ågren, H. The Journal of Chemical Physics, Vol. 136, Issue 10 https://doi.org/10.1063/1.3687002	journal	March 2012
Silicon–Carbon Bond Inversions Driven by 60-keV Electrons in Graphene Susi, Toma; Kotakoski, Jani; Kepaptsoglou, Demie Physical Review Letters, Vol. 113, Issue 11 https://doi.org/10.1103/PhysRevLett.113.115501	journal	September 2014
Electronic Structure and Stability of Semiconducting Graphene Nanoribbons Barone, Verónica; Hod, Oded; Scuseria, Gustavo E. Nano Letters, Vol. 6, Issue 12 https://doi.org/10.1021/nl0617033	journal	December 2006
Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis Vosko, S. H.; Wilk, L.; Nusair, M. Canadian Journal of Physics, Vol. 58, Issue 8 https://doi.org/10.1139/p80-159	journal	August 1980
A grid-based Bader analysis algorithm without lattice bias Tang, W.; Sanville, E.; Henkelman, G. Journal of Physics: Condensed Matter, Vol. 21, Issue 8 https://doi.org/10.1088/0953-8984/21/8/084204	journal	January 2009
Engineering single-atom dynamics with electron irradiation Su, Cong; Tripathi, Mukesh; Yan, Qing-Bo Science Advances, Vol. 5, Issue 5 https://doi.org/10.1126/sciadv.aav2252	journal	May 2019
Spin-unrestricted character of Kohn-Sham orbitals for open-shell systems Pople, John A.; Gill, Peter M. W.; Handy, Nicholas C. International Journal of Quantum Chemistry, Vol. 56, Issue 4 https://doi.org/10.1002/qua.560560414	journal	November 1995
Manipulating low-dimensional materials down to the level of single atoms with electron irradiation Susi, Toma; Meyer, Jannik C.; Kotakoski, Jani Ultramicroscopy, Vol. 180 https://doi.org/10.1016/j.ultramic.2017.03.005	journal	September 2017
Synthesis, Electronic Structure, and Raman Scattering of Phosphorus-Doped Single-Wall Carbon Nanotubes Maciel, I. O.; Campos-Delgado, J.; Cruz-Silva, E. Nano Letters, Vol. 9, Issue 6 https://doi.org/10.1021/nl9004207	journal	June 2009
Single-atom spectroscopy of phosphorus dopants implanted into graphene Susi, Toma; Hardcastle, Trevor P.; Hofsäss, Hans 2D Materials, Vol. 4, Issue 2 https://doi.org/10.1088/2053-1583/aa5e78	journal	February 2017
A fast and robust algorithm for Bader decomposition of charge density Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes Computational Materials Science, Vol. 36, Issue 3 https://doi.org/10.1016/j.commatsci.2005.04.010	journal	June 2006
Synthesis of Phosphorus-Doped Graphene and its Multifunctional Applications for Oxygen Reduction Reaction and Lithium Ion Batteries Zhang, Chenzhen; Mahmood, Nasir; Yin, Han Advanced Materials, Vol. 25, Issue 35 https://doi.org/10.1002/adma.201301870	journal	July 2013
Simulating One-Photon Absorption and Resonance Raman Scattering Spectra Using Analytical Excited State Energy Gradients within Time-Dependent Density Functional Theory Silverstein, Daniel W.; Govind, Niranjan; van Dam, Hubertus J. J. Journal of Chemical Theory and Computation, Vol. 9, Issue 12 https://doi.org/10.1021/ct4007772	journal	November 2013
Stability conditions and nuclear rotations in the Hartree-Fock theory Thouless, D. J. Nuclear Physics, Vol. 21 https://doi.org/10.1016/0029-5582(60)90048-1	journal	November 1960
Spin polarization and annihilation for radicals and diradicals Davidson, Ernest R.; Clark, Aurora E. International Journal of Quantum Chemistry, Vol. 103, Issue 1 https://doi.org/10.1002/qua.20478	journal	January 2005
Spin contamination in density functional theory Baker, Jon; Scheiner, Andrew; Andzelm, Jan Chemical Physics Letters, Vol. 216, Issue 3-6 https://doi.org/10.1016/0009-2614(93)90113-F	journal	December 1993
Self‐consistent molecular orbital methods. XVIII. Constraints and stability in Hartree–Fock theory Seeger, Rolf; Pople, John A. The Journal of Chemical Physics, Vol. 66, Issue 7 https://doi.org/10.1063/1.434318	journal	April 1977
Is the Tamm-Dancoff Approximation Reliable for the Calculation of Absorption and Fluorescence Band Shapes? Chantzis, Agisilaos; Laurent, Adèle D.; Adamo, Carlo Journal of Chemical Theory and Computation, Vol. 9, Issue 10 https://doi.org/10.1021/ct400597f	journal	September 2013
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations Valiev, M.; Bylaska, E. J.; Govind, N. Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489 https://doi.org/10.1016/j.cpc.2010.04.018	journal	September 2010
Synthesis and characterization of triangulene Pavliček, Niko; Mistry, Anish; Majzik, Zsolt Nature Nanotechnology, Vol. 12, Issue 4 https://doi.org/10.1038/nnano.2016.305	journal	February 2017
Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene Lee, C.; Wei, X.; Kysar, J. W. Science, Vol. 321, Issue 5887, p. 385-388 https://doi.org/10.1126/science.1157996	journal	July 2008
Synthetic organic spin chemistry for structurally well-defined open-shell graphene fragments Morita, Yasushi; Suzuki, Shuichi; Sato, Kazunobu Nature Chemistry, Vol. 3, Issue 3 https://doi.org/10.1038/nchem.985	journal	February 2011
Nitrogen-Doped Graphene and Its Application in Electrochemical Biosensing Wang, Ying; Shao, Yuyan; Matson, Dean W. ACS Nano, Vol. 4, Issue 4 https://doi.org/10.1021/nn100315s	journal	March 2010
Two-dimensional gas of massless Dirac fermions in graphene Novoselov, K. S.; Geim, A. K.; Morozov, S. V. Nature, Vol. 438, Issue 7065, p. 197-200 https://doi.org/10.1038/nature04233	journal	November 2005
The radical character of the acenes: A density matrix renormalization group study Hachmann, Johannes; Dorando, Jonathan J.; Avilés, Michael The Journal of Chemical Physics, Vol. 127, Issue 13 https://doi.org/10.1063/1.2768362	journal	October 2007
Half-metallicity and spin-contamination of the electronic ground state of graphene nanoribbons and related systems: An impossible compromise? Huzak, M.; Deleuze, M. S.; Hajgató, B. The Journal of Chemical Physics, Vol. 135, Issue 10 https://doi.org/10.1063/1.3626554	journal	September 2011
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Simple preparation of nanoporous few-layer nitrogen-doped graphene for use as an efficient electrocatalyst for oxygen reduction and oxygen evolution reactions Lin, Ziyin; Waller, Gordon H.; Liu, Yan Carbon, Vol. 53 https://doi.org/10.1016/j.carbon.2012.10.039	journal	March 2013
Polyradical Character of Triangular Non-Kekulé Structures, Zethrenes, p -Quinodimethane-Linked Bisphenalenyl, and the Clar Goblet in Comparison: An Extended Multireference Study Das, Anita; Müller, Thomas; Plasser, Felix The Journal of Physical Chemistry A, Vol. 120, Issue 9 https://doi.org/10.1021/acs.jpca.5b12393	journal	February 2016
Single-Reference ab Initio Methods for the Calculation of Excited States of Large Molecules Dreuw, Andreas; Head-Gordon, Martin Chemical Reviews, Vol. 105, Issue 11 https://doi.org/10.1021/cr0505627	journal	November 2005
Placing single atoms in graphene with a scanning transmission electron microscope Dyck, Ondrej; Kim, Songkil; Kalinin, Sergei V. Applied Physics Letters, Vol. 111, Issue 11 https://doi.org/10.1063/1.4998599	journal	September 2017
Nudged elastic band method for finding minimum energy paths of transitions JÓNsson, Hannes; Mills, Greg; Jacobsen, Karsten W. Proceedings of the International School of Physics, Classical and Quantum Dynamics in Condensed Phase Simulations https://doi.org/10.1142/9789812839664_0016	conference	November 2011
Atoms in molecules Bader, R. F. W. Accounts of Chemical Research, Vol. 18, Issue 1 https://doi.org/10.1021/ar00109a003	journal	January 1985
Electric Field Effect in Atomically Thin Carbon Films Novoselov, K. S. Science, Vol. 306, Issue 5696, p. 666-669 https://doi.org/10.1126/science.1102896	journal	October 2004
Quantized conductance of a suspended graphene nanoconstriction Tombros, Nikolaos; Veligura, Alina; Junesch, Juliane Nature Physics, Vol. 7, Issue 9 https://doi.org/10.1038/nphys2009	journal	June 2011
Improved All-Carbon Spintronic Device Design Bullard, Zachary; Girão, Eduardo Costa; Owens, Jonathan R. Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep07634	journal	January 2015
Phosphorus doped graphene nanosheets for room temperature NH3 sensing Niu, Fang; Tao, Li-Ming; Deng, Yu-Chao New Journal of Chemistry, Vol. 38, Issue 6 https://doi.org/10.1039/c4nj00162a	journal	January 2014
Direct visualization of the 3D structure of silicon impurities in graphene Hofer, Christoph; Skakalova, Viera; Monazam, Mohammad R. A. Applied Physics Letters, Vol. 114, Issue 5 https://doi.org/10.1063/1.5063449	journal	February 2019
Spin filter, spin amplifier and spin diode in graphene nanodisk Ezawa, M. The European Physical Journal B, Vol. 67, Issue 4 https://doi.org/10.1140/epjb/e2009-00041-7	journal	February 2009
Molecular mechanics valence bond methods for large active spaces. Application to conjugated polycyclic hydrocarbons Bearpark, Michael J.; Robb, Michael A.; Bernardi, Fernando Chemical Physics Letters, Vol. 217, Issue 5-6 https://doi.org/10.1016/0009-2614(93)E1433-H	journal	January 1994
Ultrafast electron dynamics in epitaxial graphene investigated with time- and angle-resolved photoemission spectroscopy Ulstrup, Søren; Christian Johannsen, Jens; Crepaldi, Alberto Journal of Physics: Condensed Matter, Vol. 27, Issue 16 https://doi.org/10.1088/0953-8984/27/16/164206	journal	April 2015
Towards atomically precise manipulation of 2D nanostructures in the electron microscope Susi, Toma; Kepaptsoglou, Demie; Lin, Yung-Chang 2D Materials, Vol. 4, Issue 4 https://doi.org/10.1088/2053-1583/aa878f	journal	September 2017
Direct View of Hot Carrier Dynamics in Graphene Johannsen, Jens Christian; Ulstrup, Søren; Cilento, Federico Physical Review Letters, Vol. 111, Issue 2 https://doi.org/10.1103/PhysRevLett.111.027403	journal	July 2013
Pure spin current and phonon thermoelectric transport in a triangulene-based molecular junction Wang, Qiang; Li, Jianwei; Nie, Yihang Physical Chemistry Chemical Physics, Vol. 20, Issue 23 https://doi.org/10.1039/C8CP02322K	journal	January 2018
Phosphorus-doped graphene and (8, 0) carbon nanotube: Structural, electronic, magnetic properties, and chemical reactivity Wang, Hong-mei; Wang, Hong-xia; Chen, Ying Applied Surface Science, Vol. 273 https://doi.org/10.1016/j.apsusc.2013.02.035	journal	May 2013
The First Detection of a Clar's Hydrocarbon, 2,6,10-Tri- tert -Butyltriangulene: A Ground-State Triplet of Non-Kekulé Polynuclear Benzenoid Hydrocarbon Inoue, Jun; Fukui, Kozo; Kubo, Takashi Journal of the American Chemical Society, Vol. 123, Issue 50 https://doi.org/10.1021/ja016751y	journal	December 2001
Electronic Transport and Mechanical Properties of Phosphorus- and Phosphorus−Nitrogen-Doped Carbon Nanotubes Cruz-Silva, Eduardo; López-Urías, Florentino; Muñoz-Sandoval, Emilio ACS Nano, Vol. 3, Issue 7 https://doi.org/10.1021/nn900286h	journal	June 2009
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F. The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627 https://doi.org/10.1021/j100096a001	journal	November 1994
Synthesis of a derivative of triangulene; the first non-kekulé polynuclear aromatic Allinson, Graeme; Bushby, Richard J.; Paillaud, Jean-Louis J. Chem. Soc., Perkin Trans. 1, Issue 4 https://doi.org/10.1039/P19950000385	journal	January 1995
Some reasons not to use spin projected density functional theory Wittbrodt, Joanne M.; Schlegel, H. Bernhard The Journal of Chemical Physics, Vol. 105, Issue 15 https://doi.org/10.1063/1.472497	journal	October 1996
Fate of the open-shell singlet ground state in the experimentally accessible acenes: A quantum Monte Carlo study Dupuy, Nicolas; Casula, Michele The Journal of Chemical Physics, Vol. 148, Issue 13 https://doi.org/10.1063/1.5016494	journal	April 2018
Building Structures Atom by Atom via Electron Beam Manipulation Dyck, Ondrej; Kim, Songkil; Jimenez-Izal, Elisa Small, Vol. 15, Issue 8 https://doi.org/10.1002/smll.201805310	journal	February 2019
Single-Reference ab initio Methods for the Calculation of Excited States of Large Molecules Dreuw, Andreas; Head-Gordon, Martin ChemInform, Vol. 37, Issue 5 https://doi.org/10.1002/chin.200605293	journal	January 2006
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Robert, Parr,; Chengteh, Lee,; Weitao, Yang, The University of North Carolina at Chapel Hill University Libraries https://doi.org/10.17615/zrp0-ry04	text	January 1988
The radical character of the acenes: A density matrix renormalization group study Hachmann, Johannes; Dorando, Jonathan J.; Aviles, Michael arXiv https://doi.org/10.48550/arxiv.0707.3120	text	January 2007
Quantized conductance of a suspended graphene nanoconstriction Tombros, Nikolaos; Veligura, Alina; Junesch, Juliane arXiv https://doi.org/10.48550/arxiv.1102.0434	text	January 2011
Silicon-carbon bond inversions driven by 60 keV electrons in graphene Susi, Toma; Kotakoski, Jani; Kepaptsoglou, Demie arXiv https://doi.org/10.48550/arxiv.1407.4274	text	January 2014
Fate of the open-shell singlet ground state in the experimentally accessible acenes: a quantum Monte Carlo study Dupuy, Nicolas; Casula, Michele arXiv https://doi.org/10.48550/arxiv.1804.06276	text	January 2018
Direct visualization of the 3D structure of silicon impurities in graphene Hofer, Christoph; Skakalova, Viera; Monazam, Mohammad Reza Ahmadpour arXiv https://doi.org/10.48550/arxiv.1809.08946	text	January 2018
Electric Field Effect in Atomically Thin Carbon Films Novoselov, K. S.; Geim, A. K.; Morozov, S. V. arXiv https://doi.org/10.48550/arxiv.cond-mat/0410550	text	January 2004

Similar Records

Nonadiabatic Effects on Defect Diffusion in Silicon-Doped Nanographenes

Journal Article · 2020 · Nano Letters · OSTI ID:1764479

Lingerfelt, David B.; Yu, Tao; Yoshimura, Anthony; +3 more

Moving solvated electrons with light: Nonadiabatic mixed quantum/classical molecular dynamics simulations of the relocalization of photoexcited solvated electrons in tetrahydrofuran (THF)

Journal Article · 2006 · Journal of Chemical Physics · OSTI ID:20864345

Bedard-Hearn, Michael J; Larsen, Ross E; Schwartz, Benjamin J

Nonadiabatic Molecular Dynamics Study of the Relaxation Pathways of Photoexcited Cyclooctatetraene

Journal Article · 2021 · Journal of Physical Chemistry Letters · OSTI ID:1922849

Song, Huajing; Nam, Yeonsig; Keefer, Daniel; +3 more

Related Subjects

36 MATERIALS SCIENCE
inelastic electron scattering
pyramidal defect inversion
substitutionally doped graphene
time‐dependent density functional theory

Title: Electronically Nonadiabatic Structural Transformations Promoted by Electron Beams

Citation Formats

References (65)

Similar Records

Related Subjects