Title: Structure and Thermodynamics of Li+Arn Clusters beyond the Second Solvation Shell

Authors: J. M. C. Marques and F. V. Prudente

DOI: https://doi.org/10.3390/sym16020229

Date:02/14/2024

Working Group: WG3

Grant Period: 2nd GP 2023-2024

Grant Period Goal (number): GAPG-5

Countries involved: Portugal, Brazil

Number of female/young/ITC coauthors: 1

Abstract: Small Li+Arn clusters are employed in this work as model systems to study microsolvation. Although first and second solvation shells are expected to be the most relevant ones for this type of atomic solvents, it is also interesting to explore larger clusters in order to identify the influence of external atoms on structural and thermodynamic properties. In this work, we perform a global geometry optimization for Li+Ar𝑛 clusters (with n = 41–100) and parallel tempering Monte Carlo (PTMC) simulations for some selected sizes. The results show that global minimum structures of large clusters always have 6 argon atoms in the first solvation shell while maintaining the number of 14 or 16 argon atoms in the second one. By contrast, third and fourth solvation shells vary significantly the number of argon atoms with the cluster size, and other shells can hardly be assigned due to the reduced influence of Li+ on the external argon atoms for large clusters. In turn, PTMC calculations show that the melting of the most external solvation shells of large microsolvation clusters occurs at 𝑇∼50K, which is independent of cluster size. Structural transitions can be observed between quasi-degenerated structures at low temperatures. Moreover, the present results highlight the fluxional character of the external solvation shells of these large Li+Ar𝑛 clusters, which may be seen as typical “snowball” structures.

 

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