The nature of a floating electron

Dynamics of electron solvation at the water surface is studied using extensive ab initio simulations. Calculations have been performed on semi-classical water at 300 K temperature with an excess quantum electron on its surface. It is found that after a very fast 30-50 fs initial localization, there follow fast 50-70 fs rotationally mediated transitions of the excess electron between surface trap states with a lifetime of 150-400 fs. In less then 2 ps the excess electron gets trapped in an ordered floating electron state on the surface of water with a lifetime of more than 7 ps. The excess electron diffusion coefficient and spectrum of its velocity autocorrelation function change over time to reflect a transition from a very mobile phase (first 2 ps) to a trapped floating electron phase (2-7 ps). (C) 2004 Elsevier B.V. All rights reserved.