Please use this identifier to cite or link to this item:
http://hdl.handle.net/2445/150764
Title: | Consequences of electron correlation for XPS binding energies: Representative case for C(1s) and O(1s) XPS of CO |
Author: | Bagus, Paul S. Sousa Romero, Carmen Illas i Riera, Francesc |
Keywords: | Espectroscòpia de raigs X Teoria quàntica relativista Electroestàtica X-ray spectroscopy Relativistic quantum theory Electrostatics |
Issue Date: | 2016 |
Publisher: | American Institute of Physics |
Abstract: | 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 e↵ects due to the near degeneracy of the CO(1⇡) and CO(2⇡) 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 e↵ects, 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 ⇡ 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. |
Note: | Reproducció del document publicat a: https://doi.org/10.1063/1.4964320 |
It is part of: | Journal of Chemical Physics, 2016, vol. 145, p. 144303 |
URI: | http://hdl.handle.net/2445/150764 |
Related resource: | https://doi.org/10.1063/1.4964320 |
ISSN: | 0021-9606 |
Appears in Collections: | Articles publicats en revistes (Ciència dels Materials i Química Física) |
Files in This Item:
File | Description | Size | Format | |
---|---|---|---|---|
664715.pdf | 603.31 kB | Adobe PDF | View/Open |
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.