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 Schrödinger equation formulation, we are able to provide a more comprehensive picture of the electronic energies and the coupling between solute and solvent electronic dynamics. In particular, the 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, which 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.

An open quantum system theory for polarizable continuum models / Guido, C. A.; Rosa, M.; Cammi, R.; Corni, S.. - In: JOURNAL OF CHEMICAL PHYSICS ONLINE. - ISSN 1089-7690. - 152:17(2020), p. 174114. [10.1063/5.0003523]

An open quantum system theory for polarizable continuum models

Cammi R.;
2020-01-01

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 Schrödinger equation formulation, we are able to provide a more comprehensive picture of the electronic energies and the coupling between solute and solvent electronic dynamics. In particular, the 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, which 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.
2020
An open quantum system theory for polarizable continuum models / Guido, C. A.; Rosa, M.; Cammi, R.; Corni, S.. - In: JOURNAL OF CHEMICAL PHYSICS ONLINE. - ISSN 1089-7690. - 152:17(2020), p. 174114. [10.1063/5.0003523]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/2881010
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