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Relativistic effects on Sternheimer shieldings and the polarizabilities of the electric-field gradient at the nucleus: HX (X = F,Cl,Br,I,At) and Br 2
2003 (English)In: Journal of Molecular Structure: THEOCHEM, ISSN 0166-1280, Vol. 633, no 2-3, 163-176 p.Article in journal (Refereed) Published
Abstract [en]

We investigate the relativistic effects on the electric field gradient (EFG) at the nucleus, the generalized Stemheimer shielding constants, and the EFG polarizabilities using analytic quadratic response theory at the four-component Dirac-Hartree-Fock level of theory. Particular attention is paid to the basis set requirements for calculations at the four-component level of theory of these higher-order properties involving operators that probe both the near-nucleus and the outer regions of the electron density. Our results show that relativistic effects become non-negligible for the hydrogen halides starting with hydrogen bromide and the heavier members of the group 17 halides. Interestingly, the relativistic effects are much more pronounced for the heavy-atom in hydrogen bromide, being about 10% for most of the generalized EFG polarizabilities, than in the homonuclear diatomic molecule Br2, where relativistic effects in general are much less than 10%.

Place, publisher, year, edition, pages
2003. Vol. 633, no 2-3, 163-176 p.
Keyword [en]
Dirac-Hartree-Fock, Electric field gradient at the nucleus, Electric properties, Hydrogen halides, Relativity, Stemheimer sheildings, bromine, hydrobromic acid, article, atom, electric field, electrochemistry, electron, molecular dynamics, polarization
National Category
Theoretical Chemistry
URN: urn:nbn:se:kth:diva-198800DOI: 10.1016/S0166-1280(03)00272-0ScopusID: 2-s2.0-0042971789OAI: diva2:1058929

QC 20161222

Available from: 2016-12-21 Created: 2016-12-21 Last updated: 2016-12-22Bibliographically approved

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Norman, P.
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