Solvation dynamics of the hydrated electron: A nonadiabatic quantum simulation

Abstract

A new algorithm for the quantum dynamical simulation of a mixed classical-quantum system that rigorously includes nonadiabatic quantum transitions is applied to the problem of the solvation dynamics of an initially energetic excess electron in liquid water. Computed results reveal a major channel associated with the appearance of a relatively long-lived solvated excited state postulated earlier; this state is identified as a distorted form of the equilibrium first excited state. The transient spectra evaluated directly from the simulation compare well with experimental data.