Spin-orbit coupling constants from coupled-cluster response theory
- 15 February 2000
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Physical Chemistry Chemical Physics
- Vol. 2 (5) , 965-971
- https://doi.org/10.1039/a908995k
Abstract
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 11Σ+→13Π transitions for BH and AlH and for the 11A′→13A″ and the 13A″→11A″ 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.Keywords
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