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Core-hole delocalization for modeling x-ray spectroscopies: A cautionary tale
Pohang Univ Sci & Technol POSTECH, Dept Chem, Pohang 37673, South Korea.;Nicolaus Copernicus Univ, Fac Phys, Astron & Informat, PL-87100 Torun, Poland..ORCID iD: 0000-0003-1671-8298
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-3770-9780
2022 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 156, no 21, article id 214109Article in journal (Refereed) Published
Abstract [en]

The influence of core-hole delocalization for x-ray photoelectron, x-ray absorption, and x-ray emission spectrum calculations is investigated in detail using approaches including response theory, transition-potential methods, and ground state schemes. The question of a localized/delocalized vacancy is relevant for systems with symmetrically equivalent atoms, as well as near-degeneracies that can distribute the core orbitals over several atoms. We show that the issues relating to core-hole delocalization are present for calculations considering explicit core-hole states, e.g., when using a core-excited or core-ionized reference state or for fractional occupation numbers. As electron correlation eventually alleviates the issues, but even when using coupled-cluster single-double and perturbative triple, there is a notable discrepancy between core-ionization energies obtained with localized and delocalized core-holes (0.5 eV for the carbon K-edge). Within density functional theory, the discrepancy correlates with the exchange interaction involving the core orbitals of the same spin symmetry as the delocalized core-hole. The use of a localized core-hole allows for a reasonably good inclusion of relaxation at a lower level of theory, whereas the proper symmetry solution involving a delocalized core-hole requires higher levels of theory to account for the correlation effects involved in orbital relaxation. For linear response methods, we further show that if x-ray absorption spectra are modeled by considering symmetry-unique sets of atoms, care has to be taken such that there are no delocalizations of the core orbitals, which would otherwise introduce shifts in absolute energies and relative features.

Place, publisher, year, edition, pages
AIP Publishing , 2022. Vol. 156, no 21, article id 214109
National Category
Biochemistry and Molecular Biology
Identifiers
URN: urn:nbn:se:kth:diva-316288DOI: 10.1063/5.0088195ISI: 000830421800003PubMedID: 35676123Scopus ID: 2-s2.0-85131306408OAI: oai:DiVA.org:kth-316288DiVA, id: diva2:1686981
Note

QC 20220812

Available from: 2022-08-12 Created: 2022-08-12 Last updated: 2024-03-15Bibliographically approved

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Brumboiu, Iulia EmiliaFransson, Thomas

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