Relativistic spin-orbit effects on hyperfine coupling tensors by density-functional theory

被引:76
作者
Arbuznikov, AV
Vaara, J
Kaupp, M
机构
[1] Univ Wurzburg, Inst Anorgan Chem, D-97074 Wurzburg, Germany
[2] Univ Helsinki, Dept Chem, Chem Phys Lab, FIN-00014 Helsinki, Finland
关键词
D O I
10.1063/1.1636720
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A second-order perturbation theory treatment of spin-orbit corrections to hyperfine coupling tensors has been implemented within a density-functional framework. The method uses the all-electron atomic mean-field approximation and/or spin-orbit pseudopotentials in incorporating one- and two-electron spin-orbit interaction within a first-principles framework. Validation of the approach on a set of main-group radicals and transition metal complexes indicates good agreement between all-electron and pseudopotential results for hyperfine coupling constants of the lighter nuclei in the system, except for cases in which scalar relativistic effects become important. The nonrelativistic Fermi contact part of the isotropic hyperfine coupling constants is not always accurately reproduced by the exchange-correlation functionals employed, particularly for the triplet and pi-type doublet radicals in the present work. For this reason, ab initio coupled-cluster singles and doubles with perturbative triples results for the first-order contributions have been combined in the validation calculations with the density-functional results for the second-order spin-orbit contributions. In the cases where spin-orbit corrections are of significant magnitude relative to the nonrelativistic first-order terms, they improve the agreement with experiment. Antisymmetric contributions to the hyperfine tensor arise from the spin-orbit contributions and are discussed for the IO2 radical, whereas rovibrational effects have been evaluated for RhC, NBr, and NI. (C) 2004 American Institute of Physics.
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页码:2127 / 2139
页数:13
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