An optimized semiclassical approximation for vibrational response functions

Abstract

The observables of multidimensional infrared spectroscopy may be calculated from nonlinear vibrational response functions. Fully quantum dynamical calculations of vibrational response functions are generally impractical, while completely classical calculations are qualitatively incorrect at long times. These challenges motivate the development of semiclassical approximations to quantum mechanics, which use classical mechanical information to reconstruct quantum effects. The mean-trajectory (MT) approximation is a semiclassical approach to quantum vibrational response functions employing classical trajectories linked by deterministic transitions representing the effects of the radiation-matter interaction. Previous application of the MT approximation to the third-order response function R(3)(t3, t2, t1) demonstrated that the method quantitatively describes the coherence dynamics of the t3 and t1 evolution times, but is qualitatively incorrect for the waiting-time t2 period. Here we develop an optimized version of the MT approximation by elucidating the connection between this semiclassical approach and the double-sided Feynman diagrams (2FD) that represent the quantum response. Establishing the direct connection between 2FD and semiclassical paths motivates a systematic derivation of an optimized MT approximation (OMT). The OMT uses classical mechanical inputs to accurately reproduce quantum dynamics associated with all three propagation times of the third-order vibrational response function.