Molecular dynamics and DFT study of 38-atom coinage metal clusters

Journal article, 2022

The thermal behavior of 38-atom mono-, bi-, and trimetallic clusters consisting of Cu, Ag, and Au atoms, is analyzed employing molecular dynamics simulations and DFT calculations for selected cluster compositions. Low-energy structures were singled out to perform NVT molecular dynamics simulations at several temperatures, using the Andersen thermostat for temperature control. The caloric curve is used to estimate the melting temperature and the specific heat. The pair distribution function g(r) of the solid and liquid-phase clusters is examined at different temperatures. When comparing the estimated melting points (Tm) among the monatomic clusters, the order becomes TmCu38>TmAg38>TmAu38. For bimetallic clusters, an increase of Tm is observed for Cu-Au compared to their monatomic counterparts, while the opposite occurs for Cu-Ag clusters. For trimetallic clusters, two low-energy isomers of the Cu36Ag1Au1 cluster are investigated. In this case, Tm is estimated to be 475 K, for the two isomers with the lowest-energy and second-to-lowest energy, respectively. For all the clusters studied, the pair distribution function g(r) shows that the first peak position is not shifted as an effect of temperature and its maximum value varies with composition, while the second peak essentially vanishes upon melting. The common-neighbor analysis (CNA) technique is used to analyze the local structural changes for the trimetallic clusters, again demonstrating a clear structural change upon melting. The HOMO-LUMO energy gap indicates that the trimetallic isomers' behavior is metallic, while the average binding energy show these clusters' energetic stability to be similar.