Semiclassical Nonadiabatic Dynamics with Quantum Trajectories

Vitaly A. Rassolov, University of South Carolina - Columbia
Sophya V. Garashchuk, University of South Carolina - Columbia

© Physical Review A 2005, American Physical Society

Rassolov, V. A. & Garashchuk, S. (2005). Semiclassical nonadiabetic dynamics with quantum trajectories. Physical Review A, 71, 032511.

http://dx.doi.org/10.1103/PhysRevA.71.032511

Abstract

Dynamics based on quantum trajectories with approximate quantum potential is generalized to nonadiabatic systems and its semiclassical properties are discussed. The formulation uses the mixed polar-coordinate space representation of a wave function. The polar part describes the overall time evolution of the wave-function components semiclassically using the single-surface approximate quantum potential. The coordinate part represents a complex“population” amplitude, which in case of localized coupling can be solved for quantum mechanically in an efficient manner. In the high-energy regime this is accomplished by using a small basis determined by the coupling between surfaces. An illustration is given for a typical curve-crossing problem. The energy-resolved probabilities obtained from the time evolution of two wave packets for a wide range of energies are in excellent agreement with exact results for energies above the threshold of the diabatic reaction, including the case of total nonadiabatic transition.