Structures and stability of the Cu$_{38}$ cluster at finite temperature

Abstract

The UV-visible and IR properties of the Cu38 nanocluster depend to a great extent on the temperature. Density functional theory and nanothermodynamics can be combined to compute the geometrical optimization of isomers and their spectroscopic properties in an approximate manner. In this article, we investigate entropy-driven isomer distributions of Cu38 clusters and the effect of temperature on their UV-visible and IR spectra. An extensive, systematic global search is performed on the potential and free energy surfaces of Cu38 using a two-stage strategy to identify the lowest-energy structure and its low-energy neighbors. The effects of temperature on the UV and IR spectra are considered via Boltzmann probability. The computed UV-visible and IR spectrum of each isomer is multiplied by its corresponding Boltzmann weight at finite temperature. Then, they are summed together to produce a final temperature-dependent, Boltzmann-weighted UV-visible and IR spectrum. Additionally, Molecular Dynamics simulation of the Cu38 nanocluster was performed to gain insight into the system dynamics and make a three-dimensional movie of the system with atomistic resolution. Our results show the thermal populations at the absolute temperature of Cu38 cluster, and the disordered structure that dominates at high temperatures.