Jump to main content
Jump to site search
SCHEDULED MAINTENANCE Close the message box

Maintenance work is planned for Monday 16 August 2021 from 07:00 to 23:59 (BST).

Website performance may be temporarily affected and you may not be able to access some PDFs or images. If this does happen, refreshing your web browser should resolve the issue. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 45, 2020

Assessing cluster models of solvation for the description of vibrational circular dichroism spectra: synergy between static and dynamic approaches

Author affiliations

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 (1S,2S)-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.

Graphical abstract: Assessing cluster models of solvation for the description of vibrational circular dichroism spectra: synergy between static and dynamic approaches

Supplementary files

Article information


Submitted
21 Jul 2020
Accepted
28 Oct 2020
First published
28 Oct 2020

Phys. Chem. Chem. Phys., 2020,22, 26047-26068
Article type
Perspective

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, 26047 DOI: 10.1039/D0CP03869E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.


Social activity

Search articles by author

Spotlight

Advertisements