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

TL;DR

This study combines density functional theory and nanothermodynamics to analyze how temperature influences the structure and spectroscopic properties of Cu38 nanoclusters, revealing entropy-driven isomer distributions and disordered high-temperature states.

Contribution

It introduces a systematic global search and Boltzmann-weighted spectral analysis to understand temperature effects on Cu38 clusters, integrating molecular dynamics for dynamic insights.

Findings

Temperature significantly affects Cu38 cluster spectra.

Disordered structures dominate at high temperatures.

Entropy influences isomer distribution and stability.

Abstract

The UV-visible and IR properties of the Cu$_{38}$ 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 Cu$_{38}$ 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 Cu$_{38}$ 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.