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dc.contributor.authorJakubowska, Katarzyna
dc.contributor.authorPecul-Kudelska, Magdalena
dc.contributor.authorRuud, Kenneth
dc.date.accessioned2021-12-13T14:21:07Z
dc.date.available2021-12-13T14:21:07Z
dc.date.issued2021-11-29
dc.description.abstractWe investigate the effect of relativity on harmonic vibrational frequencies. Density functional theory (DFT) calculations using the four-component Dirac–Coulomb Hamiltonian have been performed for 15 hydrides (H<sub>2</sub>X, X = O, S, Se, Te, Po; XH<sub>3</sub>, X = N, P, As, Sb, Bi; and XH<sub>4</sub>, X = C, Si, Ge, Sn, Pb) as well as for HC≡CPbH<sub>3</sub>. The vibrational frequencies have been calculated using finite differences of the molecular energy with respect to geometrical distortions of the nuclei. The influences of the choice of basis set, exchange–correlation functional, and step length for the numerical differentiation on the calculated harmonic vibrational frequencies have been tested, and the method has been found to be numerically robust. Relativistic effects are noticeable for the heavier congeners H<sub>2</sub>Te and H<<sub>2</sub>Po, SbH<sub>3</sub> and BiH<sub>3</sub>, and SnH<sub>4</sub> and PbH<sub>4</sub> and are much more pronounced for the vibrational modes with higher frequencies. Spin–orbit effects constitute a very small fraction of the total relativistic effects, except for H<sub>2</sub>Te and H<sub>2</sub>Po. For HC≡CPbH<sub>3</sub> we find that only the frequencies of the modes with large contributions from Pb displacements are significantly affected by relativity.en_US
dc.identifier.citationJakubowska, Pecul-Kudelska, Ruud. Relativistic Four-Component DFT Calculations of Vibrational Frequencies. Journal of Physical Chemistry A. 2021;125:10315-10320en_US
dc.identifier.cristinIDFRIDAID 1967362
dc.identifier.doi10.1021/acs.jpca.1c07398
dc.identifier.issn1089-5639
dc.identifier.issn1520-5215
dc.identifier.urihttps://hdl.handle.net/10037/23375
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.journalJournal of Physical Chemistry A
dc.relation.projectIDNorges forskningsråd: 262695en_US
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN/SFF/262695/Norway/Hylleraas Centre for Quantum Molecular Sciences//en_US
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright 2021 The Author(s)en_US
dc.subjectVDP::Mathematics and natural science: 400::Chemistry: 440en_US
dc.subjectVDP::Matematikk og Naturvitenskap: 400::Kjemi: 440en_US
dc.titleRelativistic Four-Component DFT Calculations of Vibrational Frequenciesen_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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