An investigation on the structure, spectroscopy, and thermodynamic aspects of clusters: A combined Parallel tempering and DFT based study

Abstract

The problem of identifying low‐energy structures of (n = 1‐6) was investigated, and the evaluation of important properties like heat capacity, solvation energy, and vertical detachment energy for each of the clusters was carried out. The problem was handled at two different theoretical levels. First, an adequately chosen empirical potential energy surface was used to account for the major interactions between the constituents of the cluster studied. Once the surface was chosen, the Parallel tempering algorithm was employed to search out the low‐energy critical points on this surface, which gave geometries at this level. To refine the structures further, these pre‐optimized structures were used as inputs for quantum chemical evaluation to complete the final refinement. To check whether the structures found were reasonable, sensitive properties like heat capacity, solvation energy, and vertical detachment energy were calculated. Then, an effort was made to understand and explain the variations in these properties with change in the cluster size. To understand the process of cluster formation further, thermodynamic aspects like △H (298.15 K), △G (298.15 K), and heat capacity (Cv) changes were also evaluated. Infrared spectroscopic features were also studied to see whether the introduction of the ion caused reasonable shifts compared to a pure water cluster.