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Title: Nonequilibrium Environment Dynamics in a Frequency-Dependent Polarizable Embedding Model

Journal Article · · Journal of Chemical Theory and Computation

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 both able 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. The effects of this frequency dependent solvent on a time- dependent model system - the Rabi oscillations of H+2 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 H+2 are fundamentally changed in the presence of a near-resonant excitation solvent.

Research Organization:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-76RL01830
OSTI ID:
1591879
Report Number(s):
PNNL-SA-138827
Journal Information:
Journal of Chemical Theory and Computation, Vol. 15, Issue 1
Country of Publication:
United States
Language:
English