Using the thermal Gaussian approximation approximation for theBoltzmann Operator in Semiclassical Initial Value Time CorrelationFunctions

Liu, Jian; Miller, William H.

doi:10.1063/1.2395941

Using the thermal Gaussian approximation approximation for theBoltzmann Operator in Semiclassical Initial Value Time CorrelationFunctions

Journal Article · Wed Sep 06 00:00:00 EDT 2006 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2395941· OSTI ID:918931

Liu, Jian; Miller, William H.

The thermal Gaussian approximation (TGA) recently developed by Mandelshtam et al has been demonstrated to be a practical way for approximating the Boltzmann operator exp(-{beta}H) for multidimensional systems. In this paper the TGA is combined with semiclassical (SC) initial value representations (IVRs) for thermal time correlation functions. Specifically, it is used with the linearized SC-IVR (LSC-IVR, equivalent to the classical Wigner model), and the 'forward-backward semiclassical dynamics' (FBSD) approximation developed by Makri et al. Use of the TGA with both of these approximate SC-IVRs allows the oscillatory part of the IVR to be integrated out explicitly, providing an extremely simple result that is readily applicable to large molecular systems. Calculation of the force-force autocorrelation for a strongly anharmonic oscillator demonstrates its accuracy, and of the velocity autocorrelation function (and thus the diffusion coefficient) of liquid neon demonstrates its applicability.

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Research Organization:: Ernest Orlando Lawrence Berkeley NationalLaboratory, Berkeley, CA (US)

Sponsoring Organization:: USDOE Director. Office of Science. Basic Energy Sciences; Office of Naval Research Grant N00014-05-1-0457, NSFCHE-0345280

DOE Contract Number:: AC02-05CH11231

OSTI ID:: 918931

Report Number(s):: LBNL--61564; BnR: KC0301020

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 22 Vol. 125; ISSN JCPSA6; ISSN 0021-9606

Country of Publication:: United States

Language:: English

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Using the thermal Gaussian approximation approximation for theBoltzmann Operator in Semiclassical Initial Value Time CorrelationFunctions

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