Analytic Non-adiabatic Couplings for Selected Configuration Interaction via Approximate Degenerate Coupled Perturbed Hartree-Fock.

Abstract

We use degenerate perturbation theory and assume that for degenerate pairs of orbitals, the coupled perturbed Hartree-Fock coefficients are symmetric in the degenerate basis to show [Formula: see text] is the only modification needed in the original molecular orbital basis. This enables us to develop efficient and accurate analytic nonadiabatic couplings between electronic states for selected configuration interactions (CIs). Even when the states belong to different irreducible representations, degenerate orbital pairs cannot be excluded by symmetry. For various excited states of carbon monoxide and trigonal planar ammonia, we benchmark the method against the full CI and find it to be accurate. We create a semi-numerical approach and use it to show that the analytic approach is correct even when a high-symmetry structure is distorted to break symmetry so that near degeneracies in orbitals occur. For a range of geometries of trigonal planar ammonia, we find that the analytic non-adiabatic couplings for selected CI can achieve sufficient accuracy using a small fraction of the full CI space.