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arXiv · 2010.13820

An Open Quantum System Theory for Polarizable Continuum Models

Ciro A. Guido·M. Rosa·R. Cammi·S. Corni
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Abstract

The problem of a solute described by Quantum Chemistry within a solvent represented as a polarizable continuum model (PCM) is here reformulated in terms of the open quantum systems (OQS) theory. Using its stochastic Schr\"{o}dinger Equation formulation, we are able to provide a more comprehensive picture of the electronic energies and of the coupling between solute and solvent electronic dynamics. In particular, OQS-PCM proves to be a unifying theoretical framework naturally including polarization and dispersion interactions, the effect of solvent fluctuations, and the non-Markovian solvent response. As such, the OQS-PCM describes the interplay between the solute and the solvent typical electronic dynamical times, and yields both the standard PCM and the so-called Born Oppenheimer solvation regime, where the solvent electronic response is considered faster than any electronic dynamics taking place in the solute. In analyzing the OQS-PCM, we obtained an expression for the solute-solvent dispersion (van der Waals) interactions that is very transparent in terms of a physical interpretation based on fluctuations and response functions. Finally, we present various numerical tests that support the theoretical findings

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Ciro A. Guido, M. Rosa, R. Cammi, S. Corni. 2020-10-26. An Open Quantum System Theory for Polarizable Continuum Models. https://doi.org/10.1063/5.0003523

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