title: Hydrated electron diffusion: the importance of hydrogen-bond dynamics.
abstract: Mixed quantum-classical molecular dynamics simulations have been used to investigate hydrated electron diffusion within the temperature range 283-400 K. The Arrhenius to non-Arrhenius behavior observed in experiments is reproduced with a transition temperature, T(t), estimated at 320 K. Above this temperature, the activation energy for diffusion is 7.5 +/- 0.3 kJ mol(-1). By computing equilibrium constants for interconversions between H-bonded and non-H-bonded configurations, we show that hydrated electron diffusion is driven by fluctuations in the H-bond network of hydrating water molecules. The computed activation energy is in fact the energy change associated with H-bond breakings. Above T(t), librational dynamics appear to dominate H-bond breakings in hydrating water molecules. Below T(t), in the non-Arrhenius region, hydrated electron diffusion is driven by both the librational and translational dynamics of the hydrating water molecules. A kinetic analysis is presented to complement the above findings.
authors.affiliation: Laboratoire de Chimie Physique, Universite de Paris-Sud XI, 91405 Orsay Cedex, France. kafui@berkeley.edu
authors.forename: Kafui A
authors.initials: KA
authors.lastname: Tay
authors.forename: Anne
authors.initials: A
authors.lastname: Boutin