Assessing cluster models of solvation for the description of vibrational circular dichroism spectra: synergy between static and dynamic approaches (original) (raw)
* Corresponding authors
a Institut des Sciences Moléculaires d’Orsay (ISMO), CNRS, Université Paris-Saclay, F-91405 Orsay, France
E-mail: anne.zehnacker-rentien@u-psud.fr
b Université Paris-Saclay, CNRS, Institut de Chimie Physique, UMR8000, 91405 Orsay, France
c PASTEUR, Département de Chimie, Ecole Normale Supérieure, PSL University, Sorbonne Université, CNRS, 75005 Paris, France
d Université Grenoble Alpes, CNRS, LiPhy, F-38000 Grenoble, France
Abstract
Solvation effects are essential for defining the shape of vibrational circular dichroism (VCD) spectra. Several approaches have been proposed to include them into computational models for calculating VCD signals, in particular those resting on the “cluster-in-a-liquid” model. Here we examine the capabilities of this ansatz on the example of flexible (1_S_,2_S_)-_trans_-1-amino-2-indanol solvated in dimethyl sulfoxide (DMSO). We compare cluster sets obtained from static calculations with results from explicit molecular dynamics (MD) trajectories based on either force field (FF) or first-principles (FP) methods. While the FFMD approach provides a broader sampling of configurational space, FPMD and time-correlation functions of dipole moments account for anharmonicity and entropy effects in the VCD calculation. They provide a means to evaluate the immediate effect of the solvent on the spectrum. This survey singles out several challenges associated with the use of clusters to describe solvation effects in systems showing shallow potential energy surfaces and non-covalent interactions. Static structures of clusters involving a limited number of solvent molecules satisfactorily capture the main effects of solvation in the bulk limit on the VCD spectra, if these structures are correctly weighted. The importance of taking into consideration their fluxionality, i.e. different solvent conformations sharing a same hydrogen bond pattern, and the limitations of small clusters for describing the solvent dynamics are discussed.
- This article is part of the themed collections:PCCP Perspectives and 2020 PCCP HOT Articles
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Article information
DOI
https://doi.org/10.1039/D0CP03869E
Article type
Perspective
Submitted
21 Jul 2020
Accepted
28 Oct 2020
First published
28 Oct 2020
Download Citation
Phys. Chem. Chem. Phys., 2020,22, 26047-26068
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Assessing cluster models of solvation for the description of vibrational circular dichroism spectra: synergy between static and dynamic approaches
K. Le Barbu-Debus, J. Bowles, S. Jähnigen, C. Clavaguéra, F. Calvo, R. Vuilleumier and A. Zehnacker,Phys. Chem. Chem. Phys., 2020, 22, 26047DOI: 10.1039/D0CP03869E
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