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
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7 May 2020
Research Article|
May 07 2020
An open quantum system theory for polarizable continuum models
Ciro A. Guido
;
Ciro A. Guido
1
Dipartimento di Scienze Chimiche, Università di Padova
, Padova, Italy
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Marta Rosa
;
Marta Rosa
1
Dipartimento di Scienze Chimiche, Università di Padova
, Padova, Italy
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Roberto Cammi
;
Roberto Cammi
2
Dipartimento di Chimica, Scienze della Vita e Sostenibilità Ambientale, Università di Parma
, Parma, Italy
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Stefano Corni
Stefano Corni
a)
1
Dipartimento di Scienze Chimiche, Università di Padova
, Padova, Italy
3
CNR Istituto Nanoscienze
, Modena, Italy
a)Author to whom correspondence should be addressed: [email protected]
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a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 152, 174114 (2020)
Article history
Received:
February 02 2020
Accepted:
April 12 2020
Citation
Ciro A. Guido, Marta Rosa, Roberto Cammi, Stefano Corni; An open quantum system theory for polarizable continuum models. J. Chem. Phys. 7 May 2020; 152 (17): 174114. https://doi.org/10.1063/5.0003523
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