A Discrete-Variable Local Diabatic Representation of Conical Intersection Dynamics.

Abstract

Conical intersections (CIs) are ubiquitous in polyatomic molecules and are responsible for a wide range of phenomena in photochemistry and photophysics. Modeling the conical intersection dynamics with adiabatic electronic states is hindered by the divergence of the first- and second-order derivative couplings at CIs due to electronic degeneracy. We introduce and implement a novel diabatic representation for exact correlated electron-nuclear wave packet dynamics through conical intersections. It directly employs the adiabatic electronic states but avoids the singular first- and second-order derivative couplings and is robust to different gauge choices of the electronic wave function phases. The reference nuclear geometries defining the adiabatic electronic states are determined by a discrete-variable representation of the nuclear coordinates. The nonadiabatic effects are accounted for by the electronic overlap matrix instead of derivative couplings as in the adiabatic representation. Illustrated by a two-mode conical intersection model, this representation captures all nonadiabatic effects, including electronic transitions, electronic coherence, and geometric phases. Thus, this representation provides a singularity-free framework for modeling ab initio conical intersection wave packet dynamics.