New ab Initio Potential Energy Surfaces for the Renner-Teller Coupled 11A′ and 11A′′ States of CH2

Abstract EN

New ab initio potential energy surfaces (PESs) for the two lowest-lying singlet 11A′ and 11A′′ electronic states of CH2, coupled by the Renner-Teller (RT) effect and meant for the spectroscopic study, are presented.

The surfaces are constructed using a dual-level strategy.

The internally contracted multireference configuration interaction calculations with the Davidson correction, using the aug-cc-pVQZ basis set, are employed to obtain 3042 points at the lower level.

The core and core-valence correlation effects are taken into account in the ab initio calculations with a modified optimized aug-cc-pCVQZ basis set for the higher-level points.

The analytical representations of these PESs, with the inclusion of the nonadiabatic RT terms, are obtained by the nonlinear least-squares fit of the calculated points to three-body expansion.

Quantum dynamical calculations are performed on these PESs, and the computed vibronic energy levels for the two singlet electronic states are in excellent agreement with experiment.