Electronic transitions with quantum trajectories. II
Courtney L. Lopreore, Róbert E. Wyatt
The quantum trajectory method (QTM) is applied to nonadiabatic electronic transitions. Equations of motion in a Lagrangian framework are derived for the probability density, velocity, position, and action functions for a discretized wave packet moving along coupled potential energy surfaces. In solving these equations of motion, we obtain agreement with exact quantum results computed by solving the time-dependent Schrödinger equation on a space-fixed grid. On each of the coupled potential energy surfaces, the dynamics of the trajectories is fully quantum mechanical, i.e., there are no “surface–hopping transitions.” We present a detailed analysis of the QTM results including density changes, complex oscillations of the wave functions, phase space analysis, and a detailed discussion of the forces that contribute to the evolution the trajectories.
The Journal of Chemical Physics•Jan 22, 2002•78 citations