Semiclassical initial value series representation in the continuum limit: Application to vibrational relaxation

Abstract

A recently formulated continuum limit semiclassical initial value series representation (SCIVR) of the quantum dynamics of dissipative systems is applied to the study of vibrational relaxation of model harmonic and anharmonic oscillator systems. As is well known, the classical dynamics of dissipative systems may be described in terms of a generalized Langevin equation. The continuum limit SCIVR uses the Langevin trajectories as input, albeit with a quantum noise rather than a classical noise. Combining this development with the forward-backward form of the prefactor-free propagator leads to a tractable scheme for computing quantum thermal correlation functions. Here we present the first implementation of this continuum limit SCIVR series method to study two model problems of vibrational relaxation. Simulations of the dissipative harmonic oscillator system over a wide range of parameters demonstrate that at most only the first two terms in the SCIVR series are needed for convergence of the correlation function. The methodology is then applied to the vibrational relaxation of a dissipative Morse oscillator. Here, too, the SCIVR series converges rapidly as the first two terms are sufficient to provide the quantum mechanical relaxation with an estimated accuracy on the order of a few percent. The results in this case are compared with computations obtained using the classical Wigner approximation for the relaxation dynamics.