Ab initio potential energy surfaces for excited states of the OCS⁺ molecular ion

Abstract

Potential energy surfaces for the , , , , ²Σ⁻ and ²Δ states of the OCS⁺ molecular ion have been calculated by the multi-reference configuration interaction method with the correlation consistent cc-pVTZ basis set. The and ²Δ surfaces are repulsive. Contour plots of the surfaces and loci of intersection are presented. Although the and surfaces are intersected by the ⁴Σ⁻ surface, spin–orbit coupling is expected to be unimportant and dissociation via non-adiabatic transitions directly from these states to the ⁴Σ⁻ surface is unlikely to be the primary mechanism.

Acknowledgement

The author is grateful to the Centre for Scientific Computing at the University of Warwick for the provision of computing facilities.