Consequences of electron correlation for XPS binding energies: Representative case for C(1s) and O(1s) XPS of CO

Bagus, Paul S.; Sousa, Carme; Illas, Francesc

doi:10.1063/1.4964320

Title: Consequences of electron correlation for XPS binding energies: Representative case for C(1s) and O(1s) XPS of CO

Journal Article · Thu Oct 13 00:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4964320· OSTI ID:1420727

;

In this paper, we present a study of the signs and the magnitudes of the errors of theoretical binding energies, BE’s, of the C(1s) and O(1s) core-levels compared to BE’s measured in X-Ray photoemission, XPS, experiments. In particular, we explain the unexpected sign of the error of the Hartree-Fock C(1s) BE, which is larger than experiment, in terms of correlation effects due to the near degeneracy of the CO(1π) and CO(2π) levels and show how taking this correlation into account leads to rather accurate predicted BE’s. We separate the initial state contributions of this near degeneracy, present for the ground state wavefunction, from the final state near degeneracy effects, present for the hole state wavefunctions. Thus, we are able to establish the importance for the core-level BE’s of initial state charge redistribution due to the π near-degeneracy. While the results for CO are interesting in their own right, we also consider whether our conclusions for CO are relevant for the analysis of XPS spectra of a wider range of molecules.

View Accepted Manuscript (Publisher)

Cite

Export

Save

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: GF2706

OSTI ID:: 1420727

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Vol. 145 Journal Issue: 14; ISSN 0021-9606

Publisher:: American Institute of PhysicsCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 31 works

Citation information provided by
Web of Science

References (22)

Self-Consistent-Field Wave Functions for Hole States of Some Ne-Like and Ar-Like Ions Bagus, P. S. Physical Review, Vol. 139, Issue 3A https://doi.org/10.1103/PhysRev.139.A619	journal	August 1965
Theory of X-Ray Satellites Åberg, Teijo Physical Review, Vol. 156, Issue 1 https://doi.org/10.1103/physrev.156.35	journal	April 1967
Localized and delocalized 1s core-holes in DFT calculations Chong, Delano P. Journal of Electron Spectroscopy and Related Phenomena, Vol. 159, Issue 1-3 https://doi.org/10.1016/j.elspec.2007.01.005	journal	June 2007
A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach Roos, Björn O.; Taylor, Peter R.; Sigbahn, Per E. M. Chemical Physics, Vol. 48, Issue 2 https://doi.org/10.1016/0301-0104(80)80045-0	journal	May 1980
Line intensities in the 3-0 band of CO and dipole moment matrix elements for the CO molecule Toth, Robert A.; Hunt, Robert H.; Plyler, Earle K. Journal of Molecular Spectroscopy, Vol. 32, Issue 1 https://doi.org/10.1016/0022-2852(69)90144-1	journal	October 1969
Koopmans' theorem for inner-shell ionization Manne, R.; Åberg, T. Chemical Physics Letters, Vol. 7, Issue 2 https://doi.org/10.1016/0009-2614(70)80309-8	journal	October 1970
Thermodynamic interpretation of chemical shifts in core-electron binding energies Jolly, William L.; Hendrickson, David N. Journal of the American Chemical Society, Vol. 92, Issue 7 https://doi.org/10.1021/ja00710a012	journal	April 1970
Prediction of core level binding energies in density functional theory: Rigorous definition of initial and final state contributions and implications on the physical meaning of Kohn-Sham energies Pueyo Bellafont, Noèlia; Bagus, Paul S.; Illas, Francesc The Journal of Chemical Physics, Vol. 142, Issue 21 https://doi.org/10.1063/1.4921823	journal	June 2015
The interpretation of XPS spectra: Insights into materials properties Bagus, Paul S.; Ilton, Eugene S.; Nelin, Connie J. Surface Science Reports, Vol. 68, Issue 2 https://doi.org/10.1016/j.surfrep.2013.03.001	journal	June 2013
Inexpensive determinations of valence virtual MOs for CI calculations Illas, Francesc; Merchan, Manuela; Pelissier, Michel Chemical Physics, Vol. 107, Issue 2-3 https://doi.org/10.1016/0301-0104(86)85014-5	journal	September 1986
Density functional theory calculation of 2p core-electron binding energies of Si, P, S, Cl, and Ar in gas-phase molecules Segala, Maximiliano; Takahata, Yuji; Chong, Delano P. Journal of Electron Spectroscopy and Related Phenomena, Vol. 151, Issue 1 https://doi.org/10.1016/j.elspec.2005.09.007	journal	March 2006
Anomalous electron correlation due to near degeneracy effects: Low-lying ionic states of Ne and Ar Bagus, Paul S.; Broer, Ria; Parmigiani, Fulvio Chemical Physics Letters, Vol. 421, Issue 1-3 https://doi.org/10.1016/j.cplett.2006.01.075	journal	April 2006
Atomic near-degeneracy for photoemission: Generality of 4f excitations Bagus, Paul S.; Broer, R.; Ilton, Eugene S. Journal of Electron Spectroscopy and Related Phenomena, Vol. 165, Issue 1-3 https://doi.org/10.1016/j.elspec.2008.07.008	journal	September 2008
A new near degeneracy effect for photoemission in transition metals Bagus, Paul S.; Broer, R.; Ilton, Eugene S. Chemical Physics Letters, Vol. 394, Issue 1-3 https://doi.org/10.1016/j.cplett.2004.06.120	journal	August 2004
Relativistic quantum chemistry: the MOLFDIR program package Visscher, L.; Visser, O.; Aerts, P. J. C. Computer Physics Communications, Vol. 81, Issue 1-2 https://doi.org/10.1016/0010-4655(94)90115-5	journal	June 1994
Interpretation of the Kohn–Sham orbital energies as approximate vertical ionization potentials Chong, D. P.; Gritsenko, O. V.; Baerends, E. J. The Journal of Chemical Physics, Vol. 116, Issue 5 https://doi.org/10.1063/1.1430255	journal	February 2002
Performance of the TPSS Functional on Predicting Core Level Binding Energies of Main Group Elements Containing Molecules: A Good Choice for Molecules Adsorbed on Metal Surfaces Pueyo Bellafont, Noèlia; Viñes, Francesc; Illas, Francesc Journal of Chemical Theory and Computation, Vol. 12, Issue 1 https://doi.org/10.1021/acs.jctc.5b00998	journal	December 2015
Core ionization potentials in carbon monoxide Smith, Steven R.; Darrah Thomas, T. Journal of Electron Spectroscopy and Related Phenomena, Vol. 8, Issue 1 https://doi.org/10.1016/0368-2048(76)80005-9	journal	January 1976
Vibrational excitation in C 1s and O 1s photoionization of CO Kempgens, B.; Maier, K.; Kivimäki, A. Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 30, Issue 21 https://doi.org/10.1088/0953-4075/30/21/005	journal	November 1997
Quelques aspects de la théorie des orbitales moléculaires Mulliken, R. S. Journal de Chimie Physique, Vol. 46 https://doi.org/10.1051/jcp/1949460497	journal	January 1949
The Direct CI Method Siegbahn, Per E. M. Methods in Computational Molecular Physics https://doi.org/10.1007/978-94-009-7200-1_7	book	January 1983
Assessment of dynamical and nondynamical correlation energy components for the beryllium-atom isoelectronic sequence Valderrama, E.; Ludeña, E. V.; Hinze, J. The Journal of Chemical Physics, Vol. 110, Issue 5 https://doi.org/10.1063/1.477970	journal	February 1999

Similar Records

Differential Many-Body Effects for Initial and Core Ionic States: Impact on XPS Spectra

Journal Article · Fri Apr 19 00:00:00 EDT 2019 · Theoretical Chemistry Accounts · OSTI ID:1420727

Bagus, Paul S.; Sousa, Carme; Illas, Francesc

XPS on Li-Battery-Related Compounds: Analysis of Inorganic SEI Phases and a Methodology for Charge Correction

Journal Article · Mon Aug 13 00:00:00 EDT 2018 · ACS Applied Energy Materials · OSTI ID:1420727

Wood, Kevin N.; Teeter, Glenn

Atomic Many-body effects in the 4f XPS of the U5+ and U4+ cations: Part II: Consequences of Orbital Relaxation

Journal Article · Sat Sep 01 00:00:00 EDT 2007 · Theoretical Chemistry Accounts, 118(3):495-502 · OSTI ID:1420727

Bagus, Paul S; Ilton, Eugene S

Title: Consequences of electron correlation for XPS binding energies: Representative case for C(1s) and O(1s) XPS of CO

Citation Formats

References (22)

Similar Records

Related Subjects