Linearized Semiclassical Initial Value Time Correlation FunctionsUsing the Thermal Gaussian Approximation: Applications to Condensed PhaseSystems

Liu, Jian; Miller, William H.

doi:10.1063/1.2774990

Title: Linearized Semiclassical Initial Value Time Correlation FunctionsUsing the Thermal Gaussian Approximation: Applications to Condensed PhaseSystems

Journal Article · Tue Jul 10 00:00:00 EDT 2007 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2774990· OSTI ID:918573

Liu, Jian; Miller, William H.

The linearized approximation to the semiclassical initial value representation (LSC-IVR) has been used together with the thermal Gaussian approximation (TGA) (TGA/LSC-IVR) to simulate quantum dynamical effects in realistic models of two condensed phase systems. This represents the first study of dynamical properties of the Ne13 Lennard-Jones (LJ) cluster in its liquid-solid phase transition region (temperature from 4 K 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 (liquid-like) than in the classical case. Liquid para-hydrogen at two thermodynamic state points (25 K 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 (PIMC) results at 25 K. 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.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Director. Office of Science. Basic Energy Sciences; Office of Naval Research Grant No N00014-05-1-0457

DOE Contract Number:: DE-AC02-05CH11231

OSTI ID:: 918573

Report Number(s):: LBNL-63535; JCPSA6; R&D Project: 401501; BnR: KC0301020; TRN: US200818%%452

Journal Information:: Journal of Chemical Physics, Vol. 127; Related Information: Journal Publication Date: 2007; ISSN 0021-9606

Country of Publication:: United States

Language:: English

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Title: Linearized Semiclassical Initial Value Time Correlation FunctionsUsing the Thermal Gaussian Approximation: Applications to Condensed PhaseSystems

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