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dc.contributor.authorKomorovsky, Stanislav
dc.contributor.authorRepisky, Michal
dc.contributor.authorMalkin, Elena
dc.contributor.authorDemissie, Taye Beyene
dc.contributor.authorRuud, Kenneth
dc.date.accessioned2016-03-07T14:38:41Z
dc.date.available2016-03-07T14:38:41Z
dc.date.issued2015-07-01
dc.description.abstractWe present an implementation of the nuclear spin–rotation (SR) constants based on the relativistic four-component Dirac–Coulomb Hamiltonian. This formalism has been implemented in the framework of the Hartree–Fock and Kohn–Sham theory, allowing assessment of both pure and hybrid exchange–correlation functionals. In the density-functional theory (DFT) implementation of the response equations, a noncollinear generalized gradient approximation (GGA) has been used. The present approach enforces a restricted kinetic balance condition for the small-component basis at the integral level, leading to very efficient calculations of the property. We apply the methodology to study relativistic effects on the spin–rotation constants by performing calculations on XHn (n = 1–4) for all elements X in the p-block of the periodic table and comparing the effects of relativity on the nuclear SR tensors to that observed for the nuclear magnetic shielding tensors. Correlation effects as described by the density-functional theory are shown to be significant for the spin–rotation constants, whereas the differences between the use of GGA and hybrid density functionals are much smaller. Our calculated relativistic spin–rotation constants at the DFT level of theory are only in fair agreement with available experimental data. It is shown that the scaling of the relativistic effects for the spin–rotation constants (varying between Z3.8 and Z4.5) is as strong as for the chemical shieldings but with a much smaller prefactor.en_US
dc.descriptionAccepted manuscript version. Published version at <a href=http://doi.org/10.1021/acs.jctc.5b00276>http://doi.org/10.1021/acs.jctc.5b00276</a>.en_US
dc.identifier.citationJournal of Chemical Theory and Computation 2015, 11(8):3729-3739en_US
dc.identifier.cristinIDFRIDAID 1290141
dc.identifier.doi10.1021/acs.jctc.5b00276
dc.identifier.issn1549-9626
dc.identifier.urihttps://hdl.handle.net/10037/8736
dc.identifier.urnURN:NBN:no-uit_munin_8285
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.projectIDNorges forskningsråd: 214095en_US
dc.relation.projectIDNorges forskningsråd: 177558en_US
dc.relation.projectIDNorges forskningsråd: 179568en_US
dc.relation.projectIDNorges forskningsråd: 191251en_US
dc.relation.projectIDNotur/NorStore: NN4654Ken_US
dc.relation.projectIDEU: 279619en_US
dc.rights.accessRightsopenAccess
dc.subjectVDP::Matematikk og Naturvitenskap: 400::Kjemi: 440::Teoretisk kjemi, kvantekjemi: 444en_US
dc.subjectVDP::Mathematics and natural science: 400::Chemistry: 440::Theoretical chemistry, quantum chemistry: 444en_US
dc.titleFour-Component Relativistic Density-Functional Theory Calculations of Nuclear Spin-Rotation Constants: Relativistic Effects in p-Block Hydridesen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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