Solvated First-Principles Excited-State Charge-Transfer Dynamics with Time-Dependent Polarizable Continuum Model and Solvent Dielectric Relaxation

Abstract

A first-principles solvated electronic dynamics method with a solvent relaxation mechanism is introduced in this work. Both solvent and solute are described and propagated in time by coupling the solvent implicit reaction field to the time-dependent electronic density of the solute molecule. Meanwhile, the solvent is allowed to relax from being optically active to a bath-like bulk medium, modeled by a time-dependent dielectric relaxation function. This real-time, time-dependent approach is shown to demonstrate aptly the drastic effect of solvent on the dynamics of the charge-transfer process, yielding results consistent with experimental observations.