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Isomorphic classical molecular dynamics model for an excess electron in a supercritical fluid

Miller, Thomas F., III (2008) Isomorphic classical molecular dynamics model for an excess electron in a supercritical fluid. Journal of Chemical Physics, 129 (19). Art. No. 194502. ISSN 0021-9606. doi:10.1063/1.3013357.

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Ring polymer molecular dynamics (RPMD) is used to directly simulate the dynamics of an excess electron in a supercritical fluid over a broad range of densities. The accuracy of the RPMD model is tested against numerically exact path integral statistics through the use of analytical continuation techniques. At low fluid densities, the RPMD model substantially underestimates the contribution of delocalized states to the dynamics of the excess electron. However, with increasing solvent density, the RPMD model improves, nearly satisfying analytical continuation constraints at densities approaching those of typical liquids. In the high-density regime, quantum dispersion substantially decreases the self-diffusion of the solvated electron. In this regime where the dynamics of the electron is strongly coupled to the dynamics of the atoms in the fluid, trajectories that can reveal diffusive motion of the electron are long in comparison to beta[h-bar].

Item Type:Article
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Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 2008 American Institute of Physics. Received 4 August 2008; accepted 14 October 2008; published 17 November 2008. The author sincerely thanks David Chandler, David Manolopoulos, and Bill Miller for helpful conversations. This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, U.S. Department of Energy under Contract No. DE-AC02-05CH11231. Supercomputing resources were provided by NERSC.
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC02-05CH11231
Subject Keywords:liquid theory, localized states, molecular dynamics method, self-diffusion
Issue or Number:19
Record Number:CaltechAUTHORS:MILjcp08
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:12771
Deposited By: Archive Administrator
Deposited On:23 Dec 2008 00:32
Last Modified:08 Nov 2021 22:32

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