Relative abundances and enantiomerization energy of the chiral Cu$_{13}$ cluster at finite temperature

TL;DR

This paper investigates the structure, enantiomerization energy, and temperature-dependent abundance of chiral Cu$_{13}$ nanoclusters using DFT and thermodynamics, revealing dominance of the global minimum across a wide temperature range.

Contribution

It introduces a combined computational approach using genetic algorithms, DFT, and thermodynamics to analyze chiral Cu$_{13}$ clusters at finite temperatures, including enantiomerization energies and relative abundances.

Findings

Chiral Cu$_{13}$ global minimum dominates from 20 to 1100 K.

Enantiomerization energy computed across a wide temperature range.

Structural energies compared at DFT and high-level reference methods.

Abstract

This study reports the lowest energy structure of bare Cu$_{13}$ nanoclusters as a pair of enantiomers for temperatures ranging from 20 to 1200 K. Moreover, we compute the enantiomerization energy for the interconversion from $\mathcal{M}$ to $\mathcal{P}$ structures in the chiral putative global minimum for temperatures ranging from 20 to 1300 K. Additionally, employing statistical thermodynamics and nanothermodynamics, we compute the Boltzmann Probability for each particular isomer as a function of temperature. To achieve that, we explore the free energy surface of the Cu$_{13}$ cluster, employing a genetic algorithm coupled with density functional theory and statistical thermodynamics. Moreover, we discuss the energetic ordering of structures computed at the DFT level and compared to high level DLPNO-CCSD(T1) reference energies, and we present chemical bonding analysis using the AdNDP method in the chiral putative global minimum. Based on the computed relative abundances, our results show that the chiral putative global minimum strongly dominates for temperatures ranging from 20 to 1100 K.