Linearized semiclassical initial value time correlation functions using the thermal Gaussian approximation: applications to condensed phase systems.
The linearized approximation to the semiclassical initial value representation (LSC-IVR) has been used together with the thermal Gaussian approximation (TGA) (TGA/LSC-IVR) [J. Liu and W. H. Miller, J. Chem. Phys. 125, 224104 (2006)] to simulate quantum dynamical effects in realistic models of two condensed phase systems. This represents the first study of dynamical properties of the Ne(13) Lennard-Jones cluster in its liquid-solid phase transition region (temperature from 4 to 14 K). Calculation of the force autocorrelation function shows considerable differences from that given by classical mechanics, namely that the cluster is much more mobile (liquidlike) than in the classical case. Liquid para-hydrogen at two thermodynamic state points (25 and 14 K under nearly zero external pressure) has also been studied. The momentum autocorrelation function obtained from the TGA/LSC-IVR approach shows very good agreement with recent accurate path integral Monte Carlo results at 25 K [A. Nakayama and N. Makri, J. Chem. Phys. 125, 024503 (2006)]. The self-diffusion constants calculated by the TGA/LSC-IVR are in reasonable agreement with those from experiment and from other theoretical calculations. These applications demonstrate the TGA/LSC-IVR to be a practical and versatile method for quantum dynamics simulations of condensed phase systems.
Liu
Jian
J
Department of Chemistry and K. S. Pitzer Center for Theoretical Chemistry, University of California, Berkeley, California 94720-1460, USA.
Miller
William H
WH