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Title: Liquid-state polaron theory of the hydrated electron revisited

The quantum path integral/classical liquid-state theory of Chandler and co-workers, created to describe an excess electron in solvent, is re-examined for the hydrated electron. The portion that models electron-water density correlations is replaced by two equations: the range optimized random phase approximation (RO-RPA), and the Donley, Rajasekaran, and Liu (DRL) approximation to the “two-chain” equation, both shown previously to describe accurately the static structure and thermodynamics of strongly charged polyelectrolyte solutions. The static equilibrium properties of the hydrated electron are analyzed using five different electron-water pseudopotentials. The theory is then compared with data from mixed quantum/classical Monte Carlo and molecular dynamics simulations using these same pseudopotentials. It is found that the predictions of the RO-RPA and DRL-based polaron theories are similar and improve upon previous theory, with values for almost all properties analyzed in reasonable quantitative agreement with the available simulation data. Also, it is found using the Larsen, Glover, and Schwartz pseudopotential that the theories give values for the solvation free energy that are at least three times larger than that from experiment.
Authors:
 [1] ;  [2] ; ;  [3]
  1. Valence4 Technologies, Arlington, Virginia 22202 (United States)
  2. Corning, Inc., Corning, New York 14830 (United States)
  3. Department of Chemistry and Geochemistry, Colorado School of Mines, Golden, Colorado 80401 (United States)
Publication Date:
OSTI Identifier:
22308992
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 2; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DENSITY; FREE ENERGY; HYDRATION; LIQUIDS; MOLECULAR DYNAMICS METHOD; MONTE CARLO METHOD; RANDOM PHASE APPROXIMATION; SIMULATION; SOLUTIONS; SOLVATED ELECTRONS; SOLVENTS; WATER