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

Abstract

We have investigated the quantum dynamics of photodetachment of an electron from closed-shell anions by pulsed light in the presence of perturbation produced 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 dynamics is followed by invoking the time-dependent Fourier grid Hamiltonian method to solve the relevant Schrödinger equation. The detachment rates in the presence of random fluctuations in the binding energy of the anion-electron and orientation of the dipole (with respect to the anion) have been computed and compared with the rates observed for an anion with fixed binding energy and a fixed orientation of the dipole. The possibility of the detached electron being captured by the perturbing dipole is also considered. The capture probability and rate are studied as functions of important system parameters. The possibility of using the model to understand the evolution of the charge-transfer-to-solvent spectrum is explored. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 79: 178–189, 2000