Non-Born-Oppenheimer path in anti-Hermitian dynamics for nonadiabatic transitions

Abstract

A serious difficulty in the semiclassical Ehrenfest theory for nonadiabatic transitions is that a path passing across the avoided crossing is forced to run on a potential averaged over comprising adiabatic potential surfaces that commit the avoided crossing. Therefore once a path passes through the crossing region, it immediately becomes incompatible with the standard view of "classical trajectory" running on an adiabatic surface. This casts a fundamental question to the theoretical structure of chemical dynamics. In this paper, we propose a non-Born-Oppenheimer path that is generated by an anti-Hermitian Hamiltonian, whose complex-valued eigenenergies can cross in their real parts and avoid crossing in the imaginary parts in the vicinity of the nonadiabatic transition region. We discuss the properties of this non-Born-Oppenheimer path and thereby show its compatibility with the Born-Oppenheimer classical trajectories. This theory not only allows the geometrical branching of the paths but gives the nonadiabatic transition amplitudes and quantum phases along the generated paths.