Free Energies of Cavity and Noncavity Hydrated Electrons Near the Instantaneous Air/Water Interface.

Abstract

The properties of the hydrated electron at the air/water interface are computed for both a cavity and a noncavity model using mixed quantum/classical molecular dynamics simulation. We take advantage of our recently developed formalism for umbrella sampling with a restrained quantum expectation value to calculate free-energy profiles of the hydrated electron's position relative to the water surface. We show that it is critical to use an instantaneous description of the air/water interface rather than the Gibbs' dividing surface to obtain accurate potentials of mean force. We find that noncavity electrons, which prefer to encompass several water molecules, avoid the interface where water molecules are scarce. In contrast, cavity models of the hydrated electron, which prefer to expel water, have a local free-energy minimum near the interface. When the cavity electron occupies this minimum, its absorption spectrum is quite red-shifted, its binding energy is significantly lowered, and its dynamics speed up quite a bit compared with the bulk, features that have not been found by experiment. The surface activity of the electron therefore serves as a useful test of cavity versus noncavity electron solvation.