Liquid-state polaron theory of the hydrated electron revisited

JP Donley and DR Heine and CA Tormey and DT Wu, JOURNAL OF CHEMICAL PHYSICS, 141, 024504 (2014).

DOI: 10.1063/1.4886195

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. (C) 2014 AIP Publishing LLC.

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