Spin-orbit coupling constants from coupled-cluster response theory

被引：89

作者：

Christiansen, O

Gauss, J

Schimmelpfennig, B

机构：

[1] Johannes Gutenberg Univ Mainz, Inst Phys Chem, D-55099 Mainz, Germany

[2] Univ Stockholm, FYSIKUM, Stockholm, Sweden

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2000年 / 2卷 / 05期

关键词：

D O I：

10.1039/a908995k

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 scheme for the calculation of spin-orbit coupling constants using coupled-cluster (CC) electronic structure methods is described based on response-theory expressions for transition properties. An implementation is reported for singlet-triplet transitions within the coupled-cluster singles and doubles (CCSD) approximation. An atomic mean-field representation of the spin-orbit interaction is used to simplify the calculation of spin-orbit coupling constants. Sample calculations are presented for spin-orbit couplings for the 1 (1)Sigma(+) --> 1 (3)Pi transitions for BH and AlH and for the 1 (1)A' --> 1 (3)A " and the 1(3)A " --> 1 (1)A " transitions for the silylenes HSiX, X=F, Cl, Br, and are compared to results obtained from full configuration interaction (FCI) calculations with the full Breit-Pauli spin-orbit operator.

引用

页码：965 / 971

页数：7

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