Electronic and geometric properties of M@Pt12 bimetallic clusters (M = Li, Na, K): A density functional theory

Abstract

Using density functional theory, this study investigates the changes that occur to the electronic and geometric properties of alkali metals doped with Pt12 clusters. The research shows that doping causes enormous changes in the geometric structure of the clusters, which makes them stable. This is particularly noticeable for K@Pt12 clusters. This research investigates frontier molecular orbitals and finds that Li@Pt12 and Na@Pt12 clusters have small Eg of 0.13 eV and 0.19 eV, respectively, which could make them better for electronic and photovoltaic uses. Analysis of spin charge density indicates that in Li@Pt12 and Na@Pt12 clusters, the Pt12 cage contributes the most spin to the electronic structures, with little to no spin contribution from Li and Na atoms, while in K@Pt12, both the K+ ion and the Pt12 cage build up the electronic structure. Charge density analysis shows alkali metals transfer electrons to the Pt12 cage, making ionic bonds in Li@Pt12 and metallic bonds in Na@Pt12, and K@Pt12 clusters, respectively. However, density of states (DOS) shows how new electronic states are created upon doping, altering the cluster's electronic properties. Furthermore, the calculation of global reactivity descriptors indicates that doping alters the chemical reactivity and kinetic stability. Clusters of K@Pt12 show enhanced hardness and stability. The results of this research provide novel insight into Pt12 clusters doped with Li, Na, and K. Furthermore, it expands the abilities of computational chemists to design materials that propel technological advancement.