Semiclassical mechanics of dissipative molecular processes: The correspondence principle and population relaxation


The relaxation of a primary system coupled weakly to a bath of environmental modes is examined from the standpoint of recent developments in the semiclassical theory of molecular bound states. Emphasis is placed upon highly excited, strongly nonlinear (but quasiperiodic) primary systems and zero temperature baths. The starting point for the analysis is a master equation for the populations of the eigenstates of the primary system. The correspondence principle provides semiclassical approximations to the transition rates, allowing quantum state populations to be calculated from classical trajectories. A second semiclassical approximation leads to an equation of motion for a probability density in the classical action variables. As h→0, this density agrees with the density generated by running an ensemble of damped classical trajectories and averaging out the angle variables; retention of terms of order h provides smoothed quantum corrections. Numerical examples of both semiclassical approximations are presented.

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Last updated on 10/07/2016