Semiclassical nonlinear response functions for coupled anharmonic vibrations

Abstract

Observables in linear and nonlinear infrared spectroscopy may be computed from vibrational response functions describing nuclear dynamics on a single electronic surface. We demonstrate that the Herman-Kluk (HK) semiclassical approximation to the quantum propagator yields an accurate representation of quantum coherence effects in linear and nonlinear response functions for coupled anharmonic oscillators. A considerable numerical price is paid for this accuracy; the calculation requires a multidimensional integral over a highly oscillatory integrand that also grows without bound as a function of evolution times. The interference among classical trajectories in the HK approximation produces quantization of good action variables. By treating this interference analytically, we develop a mean-trajectory (MT) approximation that requires only the propagation of classical trajectories linked by transitions in action. The MT approximation accurately reproduces coherence effects in response functions of coupled anharmonic oscillators in a regime in which the observables are strongly influenced by these interactions among vibrations.