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dc.contributor.authorKonecny, Lukas
dc.contributor.authorKomorovsky, Stanislav
dc.contributor.authorVicha, Jan
dc.contributor.authorRuud, Kenneth
dc.contributor.authorRepisky, Michal
dc.date.accessioned2023-03-06T12:01:29Z
dc.date.available2023-03-06T12:01:29Z
dc.date.issued2023-02-01
dc.description.abstractX-ray absorption spectroscopy (XAS) has gained popularity in recent years as it probes matter with high spatial and elemental sensitivities. However, the theoretical modeling of XAS is a challenging task since XAS spectra feature a fine structure due to scalar (SC) and spin–orbit (SO) relativistic effects, in particular near L and M absorption edges. While full four-component (4c) calculations of XAS are nowadays feasible, there is still interest in developing approximate relativistic methods that enable XAS calculations at the two-component (2c) level while maintaining the accuracy of the parent 4c approach. In this article we present theoretical and numerical insights into two simple yet accurate 2c approaches based on an (extended) atomic mean-field exact two-component Hamiltonian framework, (e)amfX2C, for the calculation of XAS using linear eigenvalue and damped response time-dependent density functional theory (TDDFT). In contrast to the commonly used one-electron X2C (1eX2C) Hamiltonian, both amfX2C and eamfX2C account for the SC and SO two-electron and exchange–correlation picture-change (PC) effects that arise from the X2C transformation. As we demonstrate on L- and M-edge XAS spectra of transition metal and actinide compounds, the absence of PC corrections in the 1eX2C approximation results in a substantial overestimation of SO splittings, whereas (e)amfX2C Hamiltonians reproduce all essential spectral features such as shape, position, and SO splitting of the 4c references in excellent agreement, while offering significant computational savings. Therefore, the (e)amfX2C PC correction models presented here constitute reliable relativistic 2c quantum-chemical approaches for modeling XAS.en_US
dc.description.sponsorshipEUen_US
dc.identifier.citationKonecny, Komorovsky, Vicha, Ruud, Repisky. Exact Two-Component TDDFT with Simple Two-Electron Picture-Change Corrections: X-ray Absorption Spectra Near L- and M-Edges of Four-Component Quality at Two-Component Cost. Journal of Physical Chemistry A. 2022en_US
dc.identifier.cristinIDFRIDAID 2130374
dc.identifier.doi10.1021/acs.jpca.2c08307
dc.identifier.issn1089-5639
dc.identifier.issn1520-5215
dc.identifier.urihttps://hdl.handle.net/10037/28683
dc.language.isoengen_US
dc.publisherTaylor and Francis Groupen_US
dc.relation.journalJournal of Physical Chemistry A
dc.relation.projectIDinfo:eu-repo/grantAgreement/ERC/H2020/945478/EU/Slovak Academic and Scientific PROgramme for experienced researchers/SASPRO 2/en_US
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright 2022 The Author(s)en_US
dc.rights.urihttps://creativecommons.org/licenses/by/4.0en_US
dc.rightsAttribution 4.0 International (CC BY 4.0)en_US
dc.titleExact Two-Component TDDFT with Simple Two-Electron Picture-Change Corrections: X-ray Absorption Spectra Near L- and M-Edges of Four-Component Quality at Two-Component Costen_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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Attribution 4.0 International (CC BY 4.0)
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