Quantum Kramers equation for energy diffusion and barrier crossing dynamics in the low-friction regime

Abstract

Based on a true phase space probability distribution function and an ensemble averaging procedure we have recently developed [Phys. Rev. E 65, 021109 (2002)] a non-Markovian quantum Kramers equation to derive the quantum rate coefficient for barrier crossing due to thermal activation and tunneling in the intermediate to strong friction regime. We complement and extend this approach to weak friction regime to derive quantum Kramers equation in energy space and the rate of decay from a metastable well. The theory is valid for arbitrary temperature and noise correlation. We show that depending on the nature of the potential there may be a net reduction of the total quantum rate below its corresponding classical value, which is in conformity with earlier observation. The method is independent of path integral approaches and takes care of quantum effects to all orders.