Journal of Chemical Physics, Vol.103, No.4, 1561-1573, 1995
A Semiclassical Self-Consistent-Field Approach to Dissipative Dynamics - The Spin-Boson Problem
A semiclassical time-dependent self-consistent-held approach for the description of dissipative quantum phenomena is proposed. The total density operator is approximated by a semiclassical ansatz, which couples the system degrees of freedom to the bath degrees of freedom in a self-consistent manner, and is thus in the spirit of a classical-path description. The capability of the approach is demonstrated by comparing semiclassical calculations for a spin-boson model with an Ohmic bath to exact path-integral calculations. It is shown that the semiclassical model nicely reproduces the complex dissipative behavior of the spin-boson model for a large range of model parameters. The validity and accuracy of the semiclassical approach is discussed in some detail. It is shown that the method is essentially based on the assumption of complete randomization of nuclear phases. In particular, the assumption of phase randomization allows one to perform the trace over the bath variables through quasiclassical sampling of the nuclear initial conditions without invoking any further approximation.
Keywords:CURVE-CROSSING PROBLEMS;WAVE-PACKET DYNAMICS;EXCITED-STATE DYNAMICS;FINITE TEMPERATURES;ELECTRON-TRANSFER;HOPPING ANALYSIS;MOLECULAR-COLLISIONS;2-STATE SYSTEM;QUANTUM DISSIPATION;CLASSICAL-MODEL