A Simple Phase Correction Makes a Big Difference in Nonadiabatic Molecular Dynamics

Abstract

The outcomes of nonadiabatic molecular dynamics (NA-MD) calculations are modulated by the parameters entering the time-dependent Schrödinger equation (TD-SE). The adiabatic states are commonly used as the basis in which the TD-SE is integrated. However, the phase inconsistencies of such states along the nuclear trajectories obtained in NA-MD simulations may render the wave function and other relevant properties ill-behaving, adversely affecting the dynamics. This work illustrates the consequence of adiabatic state phase inconsistencies in nonadiabatic Ehrenfest dynamics. A simple phase-correction approach is proposed and is demonstrated to alter the dynamics to make it consistent with the reference calculations done in the phase-consistent diabatic representation.