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Title: A thermodynamic view on the microsolvation of ions by rare gas: application to Li+ with argon
Authors: Guimarães, M. N.
Almeida, M. M. de
Marques, J. M. C. 
Prudente, F. V. 
Issue Date: 20-May-2020
Publisher: Royal Society of Chemistry
Project: info:eu-repo/grantAgreement/FCT/UID/QUI/00313/2019 
Serial title, monograph or event: Physical Chemistry Chemical Physics : PCCP
Volume: 22
Issue: 19
Abstract: We present a thermodynamic perspective of the microsolvation of ions by rare gas atoms, which is based on parallel tempering Monte Carlo (PTMC) simulations. This allows the establishment of a clear relationship between the structure of the solvation shells and the heat capacity (CV) as a function of the number of individual solvent species. The dependence of CV on the temperature allows the identification of the internal structure rearrangements and the onset of partial or total melting of the clusters. As an application, we have employed the PTMC technique to study the thermodynamic properties of clusters resulting from the microsolvation of Li+ by argon atoms. Specifically, calculations have been carried out for the clusters Li+Arn (n = 4-18, 33, 34, and 38) by applying two different potential energy surfaces (PESs): one includes only two-body interactions, while the other also incorporates three-body contributions. Whenever possible, we compare the present thermodynamic results with global optimization studies carried out previously (F. V. Prudente, J. M. C. Marques and F. B. Pereira, Phys. Chem. Chem. Phys., 2017, 19, 25707; W. S. Jesus et al., Int. J. Quantum Chem., 2019, 119, e25860). We conclude that the melting process arises for lower temperatures when the model PES accounts for three-body interactions. Additionally, we characterize the melting processes of the first and second solvation shells. For some specific clusters, structural rearrangements of the most external argon atoms are observed at very low temperatures.
DOI: 10.1039/d0cp01283a
Rights: embargoedAccess
Appears in Collections:I&D CQC - Artigos em Revistas Internacionais

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