6533b825fe1ef96bd1281d94
RESEARCH PRODUCT
Spin-orbit coupling constants from coupled-cluster response theory
Bernd SchimmelpfennigOve ChristiansenJürgen Gausssubject
Coupling constantCoupled clusterComputational chemistryChemistryOperator (physics)General Physics and AstronomyElectronic structureSpin–orbit interactionPhysical and Theoretical ChemistryAtomic physicsRepresentation (mathematics)Full configuration interactionMolecular electronic transitiondescription
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.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2000-01-01 | Physical Chemistry Chemical Physics |