Non-linear response and hydrogen bond dynamics for electron solvation in methanol

Non-equilibrium and equilibrium adiabatic mixed quantum-classical molecular dynamics computer simulations of the solvation dynamics of an excess elect ron in methanol are reported. We develop the connection between the multipl e time scales reflected in solvent response and individual physical phenome na, such as the radial collapse of the electron and structural relaxation o f the hydrogen-bonding network of the solvent. The significant role of the latter aspect appears responsible for the breakdown of the linear response approximation for the relaxation of the adiabatic ground state energy of th e excess electron. (C) 2000 Elsevier Science B.V. All rights reserved.