Photodetachment dynamics of closed-shell anions: Effects of perturbation by a strong neighboring dipole

We have investigated the quantum dynamics of photodetachment of an electron from closed-shell anions by pulsed light in the presence of perturbation p roduced by a neighboring solvent dipole. The anion is modeled by a suitable one-dimensional potential and assumed to interact with the dipolar solvent molecule through ion-dipole and ion-induced dipole interactions. The dynam ics is followed by invoking the time-dependent Fourier grid Hamiltonian met hod to solve the relevant Schrodinger equation. The detachment rates in the presence of random fluctuations in the binding energy of the anion-electro n and orientation of the dipole (with respect to the anion) have been compu ted and compared with the rates observed for an anion with fixed binding en ergy and a fixed orientation of the dipole. The possibility of the detached electron being captured by the perturbing dipole is also considered. The c apture probability and rate are studied as functions of important system pa rameters. The possibility of using the model to understand the evolution of the charge-transfer-to-solvent spectrum is explored. (C) 2000 John Wiley & Sons, Inc.