Exploration of free energy surface and thermal effects on relative population and infrared spectrum of the be6b11 flux-ional cluster

Carlos Emilano Buelna-Garcia, José Luis Cabellos*, Jesus Manuel Quiroz-Castillo, Gerardo Martinez-Guajardo, Cesar Castillo-Quevedo, Aned De-Leon-flores, Gilberto Anzueto-Sanchez, Martha Fabiola Martin-Del-campo-solis

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

Abstract

The starting point to understanding cluster properties is the putative global minimum and all the nearby local energy minima; however, locating them is computationally expensive and diffi-cult. The relative populations and spectroscopic properties that are a function of temperature can be approximately computed by employing statistical thermodynamics. Here, we investigate en-tropy-driven isomers distribution on Be6B11 clusters and the effect of temperature on their infrared spectroscopy and relative populations. We identify the vibration modes possessed by the cluster that significantly contribute to the zero-point energy. A couple of steps are considered for computing the temperature-dependent relative population: First, using a genetic algorithm coupled to density functional theory, we performed an extensive and systematic exploration of the potential/free energy surface of Be6B11 clusters to locate the putative global minimum and elucidate the low-en-ergy structures. Second, the relative populations’ temperature effects are determined by considering the thermodynamic properties and Boltzmann factors. The temperature-dependent relative populations show that the entropies and temperature are essential for determining the global minimum. We compute the temperature-dependent total infrared spectra employing the Boltzmann factor weighted sums of each isomer’s infrared spectrum and find that at finite temperature, the total infrared spectrum is composed of an admixture of infrared spectra that corresponds to the spectra of the lowest-energy structure and its isomers located at higher energies. The methodology and results describe the thermal effects in the relative population and the infrared spectra.

Original languageEnglish
Article number112
Pages (from-to)1-28
Number of pages28
JournalMaterials
Volume14
Issue number1
DOIs
StatePublished - Jan 2021

Bibliographical note

Publisher Copyright:
© 2020 by the authors.

Keywords

  • Boltzmann factors
  • Boron cluster
  • Density functional theory
  • Entropy
  • Fluxional
  • Gibbs free energy
  • Global minimum
  • Grimme’s approach (DFT-D3)
  • IR spectra
  • Infrared spectrum
  • Temperature

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