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Accurate X-ray absorption spectra near L- and M-edges from relativistic four-component damped response time-dependent density functional theory

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dc.title Accurate X-ray absorption spectra near L- and M-edges from relativistic four-component damped response time-dependent density functional theory en
dc.contributor.author Konečný, Lukáš
dc.contributor.author Vícha, Jan
dc.contributor.author Komorovský, Stanislav
dc.contributor.author Ruud, Kenneth
dc.contributor.author Repiský, Michal
dc.relation.ispartof Inorganic Chemistry
dc.identifier.issn 0020-1669 Scopus Sources, Sherpa/RoMEO, JCR
dc.date.issued 2022
utb.relation.volume 61
utb.relation.issue 2
dc.citation.spage 830
dc.citation.epage 846
dc.type article
dc.language.iso en
dc.publisher American Chemical Society
dc.identifier.doi 10.1021/acs.inorgchem.1c02412
dc.relation.uri https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c02412
dc.description.abstract The simulation of X-ray absorption spectra requires both scalar and spin-orbit (SO) relativistic effects to be taken into account, particularly near L- and M-edges where the SO splitting of core p and d orbitals dominates. Four-component Dirac-Coulomb Hamiltonian-based linear damped response time-dependent density functional theory (4c-DR-TDDFT) calculates spectra directly for a selected frequency region while including the relativistic effects variationally, making the method well suited for X-ray applications. In this work, we show that accurate X-ray absorption spectra near L-2,L-3- and M-4,M-5-edges of closed-shell transition metal and actinide compounds with different central atoms, ligands, and oxidation states can be obtained by means of 4c-DR-TDDFT. While the main absorption lines do not change noticeably with the basis set and geometry, the exchange-correlation functional has a strong influence with hybrid functionals performing the best. The energy shift compared to the experiment is shown to depend linearly on the amount of Hartee-Fock exchange with the optimal value being 60% for spectral regions above 1000 eV, providing relative errors below 0.2% and 2% for edge energies and SO splittings, respectively. Finally, the methodology calibrated in this work is used to reproduce the experimental L-2,L-3-edge X-ray absorption spectra of [RuCl2(DMSO)(2)(Im)(2)] and [WCl4(PMePh2)(2)], and resolve the broad bands into separated lines, allowing an interpretation based on ligand field theory and double point groups. These results support 4c-DR-TDDFT as a reliable method for calculating and analyzing X-ray absorption spectra of chemically interesting systems, advance the accuracy of state-of-the art relativistic DFT approaches, and provide a reference for benchmarking more approximate techniques. en
utb.faculty University Institute
dc.identifier.uri http://hdl.handle.net/10563/1010779
utb.identifier.obdid 43883261
utb.identifier.scopus 2-s2.0-85122319977
utb.identifier.wok 000737896000001
utb.identifier.pubmed 34958215
utb.identifier.coden INOCA
utb.source J-wok
dc.date.accessioned 2022-01-10T13:15:38Z
dc.date.available 2022-01-10T13:15:38Z
dc.description.sponsorship Research Council of NorwayResearch Council of Norway [315822, 252569]; Ministry of Education, Youth and Sports of the Czech Republic -DKRVO [RP/CPS/2020/006]; Slovak Grant Agency VEGAVedecka grantova agentura MSVVaS SR a SAV (VEGA) [2/0135/21, APVV-19-0516]; Slovak Grant Agency APVVSlovak Research and Development Agency [2/0135/21, APVV-19-0516]; UNINETT Sigma2, the National Infrastructure for High Performance Computing and Data Storage in Norway [NN4654K]; Ministry of Education, Youth and Sports of the Czech Republic through the e-INFRA CZ [90140]
dc.description.sponsorship RP/CPS/2020/006; NN4654K, Sigma2; Ministerstvo Školství, Mládeže a Tělovýchovy, MŠMT: 90140; Norges Forskningsråd: 252569, 315822; Vedecká Grantová Agentúra MŠVVaŠ SR a SAV, VEGA: 2/0135/21, APVV-19-0516
dc.rights Attribution 4.0 International
dc.rights.uri https://creativecommons.org/licenses/by/4.0/
dc.rights.access openAccess
utb.ou Centre of Polymer Systems
utb.contributor.internalauthor Vícha, Jan
utb.fulltext.affiliation Lukas Konecny,* Jan Vicha, Stanislav Komorovsky, Kenneth Ruud, and Michal Repisky* Corresponding Authors Lukas Konecny − Hylleraas Centre for Quantum Molecular Sciences, Department of Chemistry, University of Tromsø − The Arctic University of Norway, 9037 Tromsø, Norway; orcid.org/0000-0002-4073-7045; Email: lukas.konecny@uit.no Michal Repisky − Hylleraas Centre for Quantum Molecular Sciences, Department of Chemistry, University of Tromsø − The Arctic University of Norway, 9037 Tromsø, Norway; Email: michal.repisky@uit.no Authors Jan Vicha − Centre of Polymer Systems, Tomas Bata University, 760 01 Zlín, Czech Republic; orcid.org/0000-0003-3698-8236 Stanislav Komorovsky − Institute of Inorganic Chemistry, Slovak Academy of Sciences, SK-84536 Bratislava, Slovakia; orcid.org/0000-0002-5317-7200 Kenneth Ruud − Hylleraas Centre for Quantum Molecular Sciences, Department of Chemistry, University of Tromsø − The Arctic University of Norway, 9037 Tromsø, Norway; orcid.org/0000-0003-1006-8482
utb.fulltext.dates Received: August 7, 2021
utb.fulltext.sponsorship L.K., M.R., and K.R. acknowledge support from the Research Council of Norway through a Centre of Excellence Grant (Grant No. 252569) and a research grant (Grant No. 315822). J.V. acknowledges the support from the Ministry of Education, Youth and Sports of the Czech Republic -DKRVO (RP/CPS/2020/006). S.K. is grateful for financial support from Slovak Grant Agencies VEGA and APVV (contract nos. 2/0135/21 and APVV-19-0516) The computations were performed on resources provided by UNINETT Sigma2, the National Infrastructure for High Performance Computing and Data Storage in Norway (Grant No. NN4654K). This work was supported by the Ministry of Education, Youth and Sports of the Czech Republic through the e-INFRA CZ (ID: 90140).
utb.wos.affiliation [Vicha, Jan] Tomas Bata Univ, Ctr Polymer Syst, Zlin 76001, Czech Republic; [Komorovsky, Stanislav] Slovak Acad Sci, Inst Inorgan Chem, SK-84536 Bratislava, Slovakia; [Konecny, Lukas; Ruud, Kenneth; Repisky, Michal] Univ Tromso Arctic Univ Norway, Dept Chem, Hylleraas Ctr Quantum Mol Sci, N-9037 Tromso, Norway
utb.scopus.affiliation Hylleraas Centre for Quantum Molecular Sciences, Department of Chemistry, University of Tromsø, The Arctic University of Norway, Tromsø, 9037, Norway; Centre of Polymer Systems, Tomas Bata University, tř. Tomáše Bati 5678, Zlín, 760 01, Czech Republic; Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, Bratislava, SK-84536, Slovakia
utb.fulltext.projects 252569
utb.fulltext.projects 315822
utb.fulltext.projects RP/CPS/2020/006
utb.fulltext.projects 2/0135/21
utb.fulltext.projects APVV-19-0516
utb.fulltext.projects NN4654K
utb.fulltext.projects 90140
utb.fulltext.faculty University Institute
utb.fulltext.ou Centre of Polymer Systems
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