Geometrical and electronic properties of neutral and charged cesium clusters Csn(n=2–10): A theoretical study

Abstract

We have investigated the structure and electronic properties of cesium clusters following all electron ab initio theoretical methods based on configuration interaction, second-order Moller-Plesset (MP2) perturbation theory, and density-functional theory. Becke's three-parameter nonlocal hybrid exchange-correlation functional (B3LYP) is found to perform best on the present systems with a split valence 3-21G basis function. We have calculated the optimized geometries of neutral and singly charged cesium clusters having up to ten atoms, their binding energy per atom, ionization potentials (IPs), and adiabatic electron affinity (EA). Geometry optimizations for all the clusters are carried out without imposing any symmetry restriction. The neutral clusters having up to six atoms prefer planar structure and three-dimensional structure is preferred only when the number of atoms in a cluster is more than six. There is a good agreement between the present theoretical and reported experimental IP values for the neutral clusters with cluster size n<or=10. Calculated EA is also in good agreement with the available experimental data for the small Cs clusters. Similar calculations have also been carried out for small Rb clusters and the performance of B3LYP is equally good. Thermodynamic properties such as enthalpy and entropy for small Cs and Rb clusters have also been calculated and are well compared with the experimental data.