Cargando…

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

[Image: see text] X-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 (...

Descripción completa

Detalles Bibliográficos
Autores principales: Konecny, Lukas, Komorovsky, Stanislav, Vicha, Jan, Ruud, Kenneth, Repisky, Michal
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9923756/
https://www.ncbi.nlm.nih.gov/pubmed/36722848
http://dx.doi.org/10.1021/acs.jpca.2c08307
_version_ 1784887781784289280
author Konecny, Lukas
Komorovsky, Stanislav
Vicha, Jan
Ruud, Kenneth
Repisky, Michal
author_facet Konecny, Lukas
Komorovsky, Stanislav
Vicha, Jan
Ruud, Kenneth
Repisky, Michal
author_sort Konecny, Lukas
collection PubMed
description [Image: see text] X-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.
format Online
Article
Text
id pubmed-9923756
institution National Center for Biotechnology Information
language English
publishDate 2023
publisher American Chemical Society
record_format MEDLINE/PubMed
spelling pubmed-99237562023-02-14 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 Konecny, Lukas Komorovsky, Stanislav Vicha, Jan Ruud, Kenneth Repisky, Michal J Phys Chem A [Image: see text] X-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. American Chemical Society 2023-02-01 /pmc/articles/PMC9923756/ /pubmed/36722848 http://dx.doi.org/10.1021/acs.jpca.2c08307 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Konecny, Lukas
Komorovsky, Stanislav
Vicha, Jan
Ruud, Kenneth
Repisky, Michal
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
title 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
title_full 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
title_fullStr 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
title_full_unstemmed 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
title_short 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
title_sort 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
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9923756/
https://www.ncbi.nlm.nih.gov/pubmed/36722848
http://dx.doi.org/10.1021/acs.jpca.2c08307
work_keys_str_mv AT konecnylukas exacttwocomponenttddftwithsimpletwoelectronpicturechangecorrectionsxrayabsorptionspectranearlandmedgesoffourcomponentqualityattwocomponentcost
AT komorovskystanislav exacttwocomponenttddftwithsimpletwoelectronpicturechangecorrectionsxrayabsorptionspectranearlandmedgesoffourcomponentqualityattwocomponentcost
AT vichajan exacttwocomponenttddftwithsimpletwoelectronpicturechangecorrectionsxrayabsorptionspectranearlandmedgesoffourcomponentqualityattwocomponentcost
AT ruudkenneth exacttwocomponenttddftwithsimpletwoelectronpicturechangecorrectionsxrayabsorptionspectranearlandmedgesoffourcomponentqualityattwocomponentcost
AT repiskymichal exacttwocomponenttddftwithsimpletwoelectronpicturechangecorrectionsxrayabsorptionspectranearlandmedgesoffourcomponentqualityattwocomponentcost