A mean-field spin-orbit method applicable to correlated wavefunctions

被引:1027
作者
Hess, BA
Marian, CM
Wahlgren, U
Gropen, O
机构
[1] UNIV STOCKHOLM,INST PHYS,S-11385 STOCKHOLM,SWEDEN
[2] UNIV TROMSO,INST MATH & PHYS SCI,N-9037 TROMSO,NORWAY
关键词
D O I
10.1016/0009-2614(96)00119-4
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
Starting from the full microscopic Breit-Pauli or no-pair spin-orbit Hamiltonians, we have devised an effective one-electron spin-orbit Hamiltonian in a well defined series of approximations by averaging the two-electron contributions to the spin-orbit matrix element over the valence shell. In addition the two-electron integrals were restricted to comprise only one-centre terms. The validity of these approximations has been tested on several palladium containing compounds. Excellent agreement of the matrix elements of the mean-field operator with corresponding full results is observed; deviations amount to a few cm(-1) in absolute value or at most 0.2% on a relative scale. The newly defined mean-field operator can thus safely be employed to evaluate spin-orbit effects in transition metal containing compounds.
引用
收藏
页码:365 / 371
页数:7
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