An efficient way to incorporate the geometric phase in the time-dependent wave packet calculations in a diabatic representation.

Abstract

We present a new approach to incorporate the geometric phase in the time-dependent wave packet calculations based on the analytic diabatic potential energy matrices for two-state systems connecting via a conical intersection. The approach only requires information on the location of the conical intersection and the adiabatic potential energy surface of the ground electronic state and merely takes the same computational cost as a diabatic calculation. Demonstrations of the benchmark H + H2/HD reactions show that the new approach can accurately include the geometric phase in dynamics calculation and can be easily extended to the cold regime where the GP effects become more pronounced. Due to its simplicity and numerical efficiency, the new approach has the potential to extend the dynamics study of the geometric effects to a wide range of reaction systems.