Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments

Truhlar, Donald G.; Hiberty, Philippe C.; Shaik, Sason; Gordon, Mark S.; Danovich, David

doi:10.1002/anie.201904609

Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments

Journal Article · Fri Jul 05 00:00:00 EDT 2019 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201904609· OSTI ID:1531182

^[1]; ^[2]; ^[3]; ^[4]; ^[3]

Department of Chemistry Chemical Theory Center, and Minnesota Supercomputing Institute University of Minnesota 207 Pleasant St. SE Minneapolis MN 55455-0431 USA
Laboratoire de Chimie Physique, CNRS UMR8000, Bat. 349 Université de Paris-Sud 91405 Orsay Cédex France
Institute of Chemistry The Hebrew University of Jerusalem Givant-Ram Campus Jerusalem 9190407 Israel
Department of Chemistry Iowa State University and Ames Laboratory Ames IA 50014 USA

Abstract

Electron momentum spectroscopy, scanning tunneling microscopy, and photoelectron spectroscopy provide unique information about electronic structure, but their interpretation has been controversial. This essay discusses a framework for interpretation. Although this interpretation is not new, we believe it is important to present this framework in light of recent publications. The key point is that these experiments provide information about how the electron distribution changes upon ionization, not how electrons behave in the pre‐ionized state. Therefore, these experiments do not lead to a “selection of the correct orbitals” in chemistry and do not overturn the well‐known conclusion that both delocalized molecular orbitals and localized molecular orbitals are useful for interpreting chemical structure and dynamics. The two types of orbitals can produce identical total molecular electron densities and therefore molecular properties. Different types of orbitals are useful for different purposes.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; SC0015997

OSTI ID:: 1531182

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 36 Vol. 58; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (59)

Propagators in Quantum Chemistry Linderberg, Jan; Öhrn, Yngve https://doi.org/10.1002/0471721549	book	March 2004
The Complete Active Space Self-Consistent Field Method and its Applications in Electronic Structure Calculations Roos, Björn O. Advances in Chemical Physics https://doi.org/10.1002/9780470142943.ch7	book	January 1987
Grenzorbitale - ihre Bedeutung bei chemischen Reaktionen (Nobel-Vortrag) Fukui, Kenichi Angewandte Chemie, Vol. 94, Issue 11 https://doi.org/10.1002/ange.19820941105	journal	November 1982
Messung von Orbitalen: Provokation oder Wirklichkeit? Schwarz, W. H. Eugen Angewandte Chemie, Vol. 118, Issue 10 https://doi.org/10.1002/ange.200501333	journal	February 2006
Rasterkraftmikroskopie für die molekulare Strukturaufklärung Gross, Leo; Schuler, Bruno; Pavliček, Niko Angewandte Chemie, Vol. 130, Issue 15 https://doi.org/10.1002/ange.201703509	journal	February 2018
Plädoyer für eine duale Molekülorbital/Valenzbindungs-Kultur Hiberty, Philippe C.; Braïda, Benoît Angewandte Chemie, Vol. 130, Issue 21 https://doi.org/10.1002/ange.201710094	journal	March 2018
The Role of Frontier Orbitals in Chemical Reactions (Nobel Lecture) Fukui, Kenichi Angewandte Chemie International Edition in English, Vol. 21, Issue 11 https://doi.org/10.1002/anie.198208013	journal	November 1982
Measuring Orbitals: Provocation or Reality? Schwarz, W. H. Eugen Angewandte Chemie International Edition, Vol. 45, Issue 10 https://doi.org/10.1002/anie.200501333	journal	February 2006
Atomic Force Microscopy for Molecular Structure Elucidation Gross, Leo; Schuler, Bruno; Pavliček, Niko Angewandte Chemie International Edition, Vol. 57, Issue 15 https://doi.org/10.1002/anie.201703509	journal	February 2018
Pleading for a Dual Molecular-Orbital/Valence-Bond Culture Hiberty, Philippe C.; Braïda, Benoît Angewandte Chemie International Edition, Vol. 57, Issue 21 https://doi.org/10.1002/anie.201710094	journal	March 2018
Visualizing the Frontier Orbitals of a Conformationally Adapted Metalloporphyrin Weber-Bargioni, Alexander; Auwärter, Willi; Klappenberger, Florian ChemPhysChem, Vol. 9, Issue 1 https://doi.org/10.1002/cphc.200700600	journal	January 2008
Electron correlation: The many-body problem at the heart of chemistry: Electron Correlation: A Many-Body Problem Tew, David P.; Klopper, Wim; Helgaker, Trygve Journal of Computational Chemistry, Vol. 28, Issue 8 https://doi.org/10.1002/jcc.20581	journal	January 2007
Localizability of dynamic electron correlation Pulay, Peter Chemical Physics Letters, Vol. 100, Issue 2 https://doi.org/10.1016/0009-2614(83)80703-9	journal	September 1983
Are atoms intrinsic to molecular electronic wavefunctions? I. The FORS model Ruedenberg, Klaus; Schmidt, Michael W.; Gilbert, Mary M. Chemical Physics, Vol. 71, Issue 1 https://doi.org/10.1016/0301-0104(82)87004-3	journal	September 1982
Angle-resolved photoelectron spectroscopy of formaldehyde and methanol Keller, P. R.; Taylor, J. W.; Grimm, F. A. Chemical Physics, Vol. 90, Issue 1-2 https://doi.org/10.1016/0301-0104(84)85090-9	journal	October 1984
The valence orbital momentum distributions and binding energy spectra of methane by electron momentum spectroscopy: Quantitative comparisons using near Hartree-Fock limit and correlated wavefunctions Clark, S. A. C.; Reddish, T. J.; Brion, C. E. Chemical Physics, Vol. 143, Issue 1 https://doi.org/10.1016/0301-0104(90)85001-D	journal	May 1990
Seeing molecular orbitals Pascual, J. I.; Gómez-Herrero, J.; Rogero, C. Chemical Physics Letters, Vol. 321, Issue 1-2 https://doi.org/10.1016/S0009-2614(00)00337-7	journal	April 2000
Über die Zuordnung von Wellenfunktionen und Eigenwerten zu den Einzelnen Elektronen Eines Atoms Koopmans, T. Physica, Vol. 1, Issue 1-6 https://doi.org/10.1016/S0031-8914(34)90011-2	journal	January 1934
Imaging of orbital electron densities by electron momentum spectroscopy – a chemical interpretation of the binary (e,2e) reaction Brion, C. E.; Cooper, G.; Zheng, Y. Chemical Physics, Vol. 270, Issue 1 https://doi.org/10.1016/S0301-0104(01)00385-8	journal	July 2001
Electron Propagator Theory Corzo, Héctor H.; Ortiz, J. Vince Advances in Quantum Chemistry https://doi.org/10.1016/bs.aiq.2016.05.001	book	July 2016
STM images of a large organic molecule adsorbed on a bare metal substrate or on a thin insulating layer: Visualization of HOMO and LUMO Villagomez, Carlos Javier; Zambelli, Tomaso; Gauthier, Sébastien Surface Science, Vol. 603, Issue 10-12 https://doi.org/10.1016/j.susc.2008.10.057	journal	June 2009
Linear-Scaling Coupled Cluster with Perturbative Triple Excitations: The Divide–Expand–Consolidate CCSD(T) Model Eriksen, Janus J.; Baudin, Pablo; Ettenhuber, Patrick Journal of Chemical Theory and Computation, Vol. 11, Issue 7 https://doi.org/10.1021/acs.jctc.5b00086	journal	June 2015
Can Orbitals Really Be Observed in Scanning Tunneling Microscopy Experiments? Pham, Buu Q.; Gordon, Mark S. The Journal of Physical Chemistry A, Vol. 121, Issue 26 https://doi.org/10.1021/acs.jpca.7b05789	journal	June 2017
Energy Ordering of Molecular Orbitals Puschnig, P.; Boese, A. D.; Willenbockel, M. The Journal of Physical Chemistry Letters, Vol. 8, Issue 1 https://doi.org/10.1021/acs.jpclett.6b02517	journal	December 2016
Generalized valence bond description of bonding in low-lying states of molecules Goddard, William A.; Dunning, Thom H.; Hunt, William J. Accounts of Chemical Research, Vol. 6, Issue 11 https://doi.org/10.1021/ar50071a002	journal	November 1973
Classical Valence Bond Approach by Modern Methods Wu, Wei; Su, Peifeng; Shaik, Sason Chemical Reviews, Vol. 111, Issue 11 https://doi.org/10.1021/cr100228r	journal	November 2011
Have Orbitals Really Been Observed? Scerri, Eric R. Journal of Chemical Education, Vol. 77, Issue 11 https://doi.org/10.1021/ed077p1492	journal	November 2000
Is It Time To Retire the Hybrid Atomic Orbital? Grushow, Alexander Journal of Chemical Education, Vol. 88, Issue 7 https://doi.org/10.1021/ed100155c	journal	July 2011
Are Molecular Orbitals Delocalized? Truhlar, Donald G. Journal of Chemical Education, Vol. 89, Issue 5 https://doi.org/10.1021/ed200565h	journal	February 2012
In Defense of the Hybrid Atomic Orbitals Hiberty, Philippe C.; Volatron, François; Shaik, Sason Journal of Chemical Education, Vol. 89, Issue 5 https://doi.org/10.1021/ed200615j	journal	February 2012
Chemical Binding in the Water Molecule ^1a Edmiston, Clyde; Ruedenberg, Klaus The Journal of Physical Chemistry, Vol. 68, Issue 7 https://doi.org/10.1021/j100789a002	journal	July 1964
What Do the Kohn−Sham Orbitals and Eigenvalues Mean? Stowasser, Ralf; Hoffmann, Roald Journal of the American Chemical Society, Vol. 121, Issue 14 https://doi.org/10.1021/ja9826892	journal	April 1999
Koopmans’ Theorem in the Restricted Open-Shell Hartree−Fock Method. 1. A Variational Approach ^† Plakhutin, Boris N.; Davidson, Ernest R. The Journal of Physical Chemistry A, Vol. 113, Issue 45 https://doi.org/10.1021/jp9002593	journal	November 2009
Density Functional Theory of Electronic Structure Kohn, W.; Becke, A. D.; Parr, R. G. The Journal of Physical Chemistry, Vol. 100, Issue 31 https://doi.org/10.1021/jp960669l	journal	January 1996
Direct observation of d-orbital holes and Cu–Cu bonding in Cu2O Zuo, J. M.; Kim, M.; O'Keeffe, M. Nature, Vol. 401, Issue 6748 https://doi.org/10.1038/43403	journal	September 1999
Tomographic imaging of molecular orbitals Itatani, J.; Levesque, J.; Zeidler, D. Nature, Vol. 432, Issue 7019 https://doi.org/10.1038/nature03183	journal	December 2004
Recent advances in submolecular resolution with scanning probe microscopy Gross, Leo Nature Chemistry, Vol. 3, Issue 4 https://doi.org/10.1038/nchem.1008	journal	March 2011
Real-space imaging of interfacial water with submolecular resolution Guo, Jing; Meng, Xiangzhi; Chen, Ji Nature Materials, Vol. 13, Issue 2 https://doi.org/10.1038/nmat3848	journal	January 2014
A survey of the principles determining the structure and properties of molecules. Part 1.—The factors responsible for molecular shape and bond energies Lennard–Jones, John; Pople, J. A. Discuss. Faraday Soc., Vol. 10, Issue 0 https://doi.org/10.1039/DF9511000009	journal	January 1951
Split-localized orbitals can yield stronger configuration interaction convergence than natural orbitals Bytautas, Laimutis; Ivanic, Joseph; Ruedenberg, Klaus The Journal of Chemical Physics, Vol. 119, Issue 16 https://doi.org/10.1063/1.1610434	journal	October 2003
Improved Quantum Theory of Many‐Electron Systems. V. The Spin‐Coupling Optimized GI Method Ladner, Robert C.; Goddard, William A. The Journal of Chemical Physics, Vol. 51, Issue 3 https://doi.org/10.1063/1.1672106	journal	August 1969
Hindered Rotation, Hellmann—Feynmann Theorem, and Localized Molecular Orbitals Ruedenberg, Klaus The Journal of Chemical Physics, Vol. 41, Issue 2 https://doi.org/10.1063/1.1725928	journal	July 1964
Natural Expansion of Exact Wavefunctions. II. The Hydrogen‐Molecule Ground State Davidson, Ernest R.; Jones, Leon L. The Journal of Chemical Physics, Vol. 37, Issue 12 https://doi.org/10.1063/1.1733126	journal	December 1962
Dyson orbitals for ionization from the ground and electronically excited states within equation-of-motion coupled-cluster formalism: Theory, implementation, and examples Melania Oana, C.; Krylov, Anna I. The Journal of Chemical Physics, Vol. 127, Issue 23 https://doi.org/10.1063/1.2805393	journal	December 2007
The two faces of static correlation Hollett, Joshua W.; Gill, Peter M. W. The Journal of Chemical Physics, Vol. 134, Issue 11 https://doi.org/10.1063/1.3570574	journal	March 2011
Correlation‐consistent configuration interaction: Accurate bond dissociation energies from simple wave functions Carter, Emily A.; Goddard, William A. The Journal of Chemical Physics, Vol. 88, Issue 5 https://doi.org/10.1063/1.453957	journal	March 1988
Imaging the wave functions of adsorbed molecules Luftner, D.; Ules, T.; Reinisch, E. M. Proceedings of the National Academy of Sciences, Vol. 111, Issue 2 https://doi.org/10.1073/pnas.1315716110	journal	December 2013
Spin-coupled valence bond theory Cooper, D. L.; Gerratt, J.; Raimondi, M. International Reviews in Physical Chemistry, Vol. 7, Issue 1 https://doi.org/10.1080/01442358809353205	journal	January 1988
Attosecond electronic and nuclear quantum photodynamics of ozone: time-dependent Dyson orbitals and dipole Perveaux, A.; Lauvergnat, D.; Lasorne, B. Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 47, Issue 12 https://doi.org/10.1088/0953-4075/47/12/124010	journal	June 2014
Angle resolved photoemission from organic semiconductors: orbital imaging beyond the molecular orbital interpretation Dauth, M.; Wiessner, M.; Feyer, V. New Journal of Physics, Vol. 16, Issue 10 https://doi.org/10.1088/1367-2630/16/10/103005	journal	October 2014
Properties of the One-Particle Green's Function for Nonuniform Many-Fermion Systems Layzer, A. J. Physical Review, Vol. 129, Issue 2 https://doi.org/10.1103/PhysRev.129.897	journal	January 1963
The S Matrix in Quantum Electrodynamics Dyson, F. J. Physical Review, Vol. 75, Issue 11 https://doi.org/10.1103/PhysRev.75.1736	journal	June 1949
Assessment of Kohn-Sham density-functional orbitals as approximate Dyson orbitals for the calculation of electron-momentum-spectroscopy scattering cross sections Duffy, Patrick; Chong, Delano P.; Casida, Mark E. Physical Review A, Vol. 50, Issue 6 https://doi.org/10.1103/PhysRevA.50.4707	journal	December 1994
Direct Observation of Molecular Orbitals of Pentacene Physisorbed on Au(111) by Scanning Tunneling Microscope Soe, W. -H.; Manzano, C.; De Sarkar, A. Physical Review Letters, Vol. 102, Issue 17 https://doi.org/10.1103/PhysRevLett.102.176102	journal	May 2009
Molecules on Insulating Films: Scanning-Tunneling Microscopy Imaging of Individual Molecular Orbitals Repp, Jascha; Meyer, Gerhard; Stojković, Sladjana M. Physical Review Letters, Vol. 94, Issue 2 https://doi.org/10.1103/PhysRevLett.94.026803	journal	January 2005
Controlling High Harmonic Generation with Molecular Wave Packets Itatani, J.; Zeidler, D.; Levesque, J. Physical Review Letters, Vol. 94, Issue 12 https://doi.org/10.1103/PhysRevLett.94.123902	journal	March 2005
Localized Atomic and Molecular Orbitals Edmiston, Clyde; Ruedenberg, Klaus Reviews of Modern Physics, Vol. 35, Issue 3 https://doi.org/10.1103/RevModPhys.35.457	journal	July 1963
Reconstruction of Molecular Orbital Densities from Photoemission Data Puschnig, P.; Berkebile, S.; Fleming, A. J. Science, Vol. 326, Issue 5953 https://doi.org/10.1126/science.1176105	journal	September 2009
An investigation of hybridization and the orbital models of molecular electronic structure for CH ₄ , NH ₃ , and H ₂ O Brion, C. E.; Wolfe, Saul; Shi, Zheng Canadian Journal of Chemistry, Vol. 95, Issue 12 https://doi.org/10.1139/cjc-2017-0450	journal	December 2017

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