We present a semiclassically approximate quantum treatment of solvation with the purpose of investigating the accuracy of the Caldeira– Leggett model. We do that by simulating the vibrational features of water solvation by means of two different approaches. One is entirely based on the adoption of an accurate ab initio potential to describe water clusters of increasing dimensionality. The other one consists of a model made of a central water molecule coupled to a high-dimensional Caldeira–Leggett harmonic bath. We demonstrate the role of quantum effects in the detection of water solvation and show that the computationally cheap approach based on the Caldeira–Leggett bath is only partially effective. The main conclusion of the study is that quantum methods associated with high-level potential energy surfaces are necessary to correctly study solvation features, while simplified models, even if attractive owing to their reduced computational cost, can provide some useful insights but are not able to come up with a comprehensive description of the solvation phenomenon.

Caldeira–Leggett model vs ab initio potential: A vibrational spectroscopy test of water solvation / A. Rognoni, R. Conte, M. Ceotto. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 154:9(2021 Mar 01). [10.1063/5.0040494]

Caldeira–Leggett model vs ab initio potential: A vibrational spectroscopy test of water solvation

A. Rognoni
Primo
;
R. Conte
Secondo
;
M. Ceotto
Ultimo
2021

Abstract

We present a semiclassically approximate quantum treatment of solvation with the purpose of investigating the accuracy of the Caldeira– Leggett model. We do that by simulating the vibrational features of water solvation by means of two different approaches. One is entirely based on the adoption of an accurate ab initio potential to describe water clusters of increasing dimensionality. The other one consists of a model made of a central water molecule coupled to a high-dimensional Caldeira–Leggett harmonic bath. We demonstrate the role of quantum effects in the detection of water solvation and show that the computationally cheap approach based on the Caldeira–Leggett bath is only partially effective. The main conclusion of the study is that quantum methods associated with high-level potential energy surfaces are necessary to correctly study solvation features, while simplified models, even if attractive owing to their reduced computational cost, can provide some useful insights but are not able to come up with a comprehensive description of the solvation phenomenon.
Settore CHIM/02 - Chimica Fisica
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/829744
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