Nonequilibrium Environment Dynamics in a Frequency-Dependent Polarizable Embedding Model.

Abstract

Hybrid quantum mechanical/molecular mechanical (QM/MM) models are some of the most powerful and computationally feasible approaches to account for solvent effects or more general environmental perturbations on quantum chemical systems. In their more recent formulations (known as polarizable embedding) they can account for electrostatic and mutual polarization effects between the QM and the MM subsystems. In this paper, a polarizable embedding scheme based on induced dipoles that is able both to describe electron evolution of the embedded QM system in an efficient manner as well as to capture the frequency dependent behavior of the solvent is proposed, namely, ωMMPol. The effects of this frequency-dependent solvent on a time-dependent model system-the Rabi oscillations of H2+ in a resonant field-are considered. The solvent is shown to introduce only mild perturbations when the excitation frequencies of the solvent and the solute are off-resonant. However, the dynamics of the H2+ are fundamentally changed in the presence of a near-resonant excitation solvent. The effectiveness of ωMMPol to simulating realistic chemical systems is demonstrated by capturing charge transfer dynamics within a solvated system.