Theoretical prediction of structures, vibrational circular dichroism, and infrared spectra of chiral be4b8 cluster at different temperatures

Carlos Emiliano Buelna-García, Eduardo Robles-Chaparro, Tristan Parra-Arellano, Jesus Manuel Quiroz-Castillo, Teresa Del-Castillo-Castro, Gerardo Martínez-Guajardo, Cesar Castillo-Quevedo, Aned De-León-flores, Gilberto Anzueto-Sánchez, Martha Fabiola Martin-Del-campo-solis, Ana Maria Mendoza-Wilson, Alejandro Vásquez-Espinal, Jose Luis Cabellos*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

Lowest-energy structures, the distribution of isomers, and their molecular properties depend significantly on geometry and temperature. Total energy computations using DFT methodology are typically carried out at a temperature of zero K; thereby, en-tropic contributions to the total energy are neglected, even though functional materials work at finite temperatures. In the present study, the probability of the occurrence of one particular Be4B8 isomer at temperature T is estimated by employing Gibbs free energy computed within the framework of quantum statistical mechanics and nanothermody-namics. To identify a list of all possible low-energy chiral and achiral structures, an ex-haustive and efficient exploration of the potential/free energy surfaces is carried out using a multi-level multistep global genetic algorithm search coupled with DFT. In addition, we discuss the energetic ordering of structures computed at the DFT level against single-point energy calculations at the CCSD(T) level of theory. The total VCD/IR spectra as a function of temperature are computed using each isomer’s probability of occurrence in a Boltzmann-weighted superposition of each isomer’s spectrum. Additionally, we present chemical bonding analysis using the adaptive natural density partitioning method in the chiral putative global minimum. The transition state structures and the enantiomer–en-antiomer and enantiomer–achiral activation energies as a function of temperature evidence that a change from an endergonic to an exergonic type of reaction occurs at a temperature of 739 K.

Original languageEnglish
Article number3953
JournalMolecules
Volume26
Issue number13
DOIs
StatePublished - 1 Jul 2021

Bibliographical note

Publisher Copyright:
© 2021 by the authors. Licensee MDPI, Basel, Switzerland.

Keywords

  • Adaptive natural density partitioning method
  • Be4B8
  • Beryllium–boron cluster
  • Boltzmann factors
  • Density functional theory
  • Enthalpy
  • Entropy
  • Genetic algorithm
  • Gibbs free energy
  • Global minimum
  • IR spectra
  • Nanothermodynamics
  • Quantum statistical mechanics
  • Tempera-ture
  • Thermochemistry
  • Vibrational circular dichroism

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