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Dimerization dynamics of carboxylic acids in helium nanodroplets

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journal contribution
posted on 2022-06-21, 10:08 authored by AM Ellis, JA Davies, E Yurtsever, F Calvo
The dimerization of molecules in helium nanodroplets is known to preferentially yield structures of higher energy than the global energy minimum structure for a number of quite different monomers. Here, we explore dimerization in this environment using an atomistic model within statistically converged molecular dynamics (MD) trajectories, treating the solvent implicitly through the use of a thermostat, or more explicitly by embedding one monomer in a He100 cluster. The focus is on the two simplest carboxylic acids, formic and acetic, both of which have been studied experimentally. While the global minimum structure, which comprises two CO⋯HO hydrogen bonds, is predicted to be the most abundant dimer in the absence of the helium solvent, this is no longer the case once helium atoms are included. The simulations confirm the importance of kinetic trapping effects and also shed light on the occurrence of specific dynamical effects, leading to the occasional formation of high-energy structures away from minima, such as saddle configurations. Theoretically predicted infrared spectra, based on the MD statistics, are in good agreement with the experimental spectra.

History

Citation

J. Chem. Phys. 156, 174304 (2022); https://doi.org/10.1063/5.0087957

Author affiliation

School of Chemistry, University of Leicester

Version

  • AM (Accepted Manuscript)

Published in

The Journal of chemical physics

Volume

156

Issue

17

Pagination

174304

Publisher

AIP Publishing

issn

0021-9606

eissn

1089-7690

Acceptance date

2022-04-01

Copyright date

2022

Available date

2022-06-21

Spatial coverage

United States

Language

eng

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