Journal of Chemical Physics, Vol.110, No.12, 5851-5860, 1999
Coherent nuclear motion in a condensed-phase environment: Wave-packet approach and pump-probe spectroscopy
A quantum-mechanical Gaussian wave-packet approach to the theoretical description of nuclear motions in a condensed-phase environment is developed. General expressions for the time-dependent reduced density matrix are given for a harmonic potential surface, and the exact quantum dynamics is found for a microscopic system-plus-bath model. Particular attention is devoted to the influence of initial correlations between system and bath for the outcome of a pump-probe experiment. We show that the standard factorized preparation, compared to a more realistic correlated preparation, leads to significantly different stimulated emission spectra at high temperatures. Recent experiments for the reaction center are analyzed using this formalism.