CabellosResearch Group

Area 02

Finite-temperature effects and statistical thermodynamics

Free-energy surfaces, Boltzmann populations and temperature-dependent IR and VCD spectra that explain cluster fluxionality and chirality.

  • free energy
  • Boltzmann populations
  • IR spectroscopy
  • VCD
  • fluxionality
Plot of relative population versus temperature, from 0 to 1500 K, for the isomers of the anionic Be6B11 cluster computed at PBE0/Def2TZVP/GD3; isomer 1 dominates at low temperature and isomer 8 above roughly 800 K.
Boltzmann populations of the Be6B11− isomers between 0 and 1500 K. Fig. 4 from Buelna-Garcia et al., Materials (2020). CC BY 4.0

Most calculations describe molecules at 0 K, but experiments are carried out at finite temperature. At room temperature a cluster can be a mixture of isomers whose proportions change with temperature, and that changes what is observed in the laboratory.

This line builds free-energy surfaces from statistical thermodynamics and computes the Boltzmann populations of each isomer as a function of temperature. These populations are then used to average infrared (IR) and vibrational circular dichroism (VCD) spectra so they can be compared directly with experiments.

Questions addressed

  • At what temperature does the dominant structure of a cluster change?
  • How does temperature affect the enantiomerization energy of a chiral cluster?
  • Which isomers explain an experimental spectrum measured at a given temperature?

The approach has been applied to systems such as Au₁₀, Cu₁₃, Be₆B₁₁⁻ and Be₄B₈, and is complemented by ab initio molecular dynamics.

Publications in this area

14 publications

  • Francisco Eduardo Rojas-González, César Castillo-Quevedo, Peter Ludwig Rodríguez-Kessler, José Oscar Carlos Jimenez-Halla, Alejandro Vásquez-Espinal, Rajagopal Dashinamoorthy Eithiraj, Manuel Cortez-Valadez, José Luis Cabellos

    Exploration of Free Energy Surface of the Au10 Nanocluster at Finite Temperature

    Molecules 29(14), 3374 (2024)

    doi:10.3390/molecules29143374

  • Aned de Leon, José Luis Cabellos, César Castillo-Quevedo, Martha Fabiola Martín-del-Campo-Solís, Gerardo Martínez-Guajardo

    The Role of Nitrogen-Rich Moieties in the Selection of Arginine’s Tautomeric Form at Different Temperatures

    Acta Chimica Slovenica 70(4), 642–650 (2023)

    PDFdoi:10.17344/acsi.2023.8435

  • Cesar Castillo-Quevedo, Carlos Emiliano Buelna-Garcia, Edgar Paredes-Sotelo, Eduardo Robles-Chaparro, Edgar Zamora-Gonzalez, Martha Fabiola Martin-del-Campo-Solis, Jesus Manuel Quiroz-Castillo, Teresa del-Castillo-Castro, Gerardo Martínez-Guajardo, Aned de-Leon-Flores, Manuel Cortez-Valadez, Filiberto Ortiz-Chi, Tulio Gaxiola, Santos Jesus Castillo, Alejandro Vásquez-Espinal, Sudip Pan, Jose Luis Cabellos

    Effects of Temperature on Enantiomerization Energy and Distribution of Isomers in the Chiral Cu13 Cluster

    Prime Archives in Material Science (2022)Chapter

    PDFdoi:10.37247/pams4ed.4.22.16

  • Martha Fabiola Martin-del-Campo-Solis, Edgar O. Zamora Gonzales, César Castillo-Quevedo, Emiliano Buelna-Garcia, Aned de León Flores, José Luis Cabellos

    Thermodynamic Properties of Cu38 Cluster

    Prime Archives in Chemistry (2022)Chapter

    PDFdoi:10.37247/pachem2ed.2.22.22

  • Carlos Emiliano Buelna-García, Cesar Castillo-Quevedo, Jesus Manuel Quiroz-Castillo, Edgar Paredes-Sotelo, Manuel Cortez-Valadez, Martha Fabiola Martin-del-Campo-Solis, Tzarara López-Luke, Marycarmen Utrilla-Vázquez, Ana Maria Mendoza-Wilson, Peter L. Rodríguez-Kessler, Alejandro Vazquez-Espinal, Sudip Pan, Aned de Leon-Flores, Jhonny Robert Mis-May, Adán R. Rodríguez-Domínguez, Gerardo Martínez-Guajardo, Jose Luis Cabellos

    Relative Populations and IR Spectra of Cu38 Cluster at Finite Temperature Based on DFT and Statistical Thermodynamics Calculations

    Frontiers in Chemistry 10, 841964 (2022)

    PDFdoi:10.3389/fchem.2022.841964

  • Carlos Emilano Buelna-Garcia, Cesar Castillo-Quevedo, Edgar Paredes-Sotelo, Gerardo Martinez-Guajardo, Jose Luis Cabellos

    Boltzmann Populations of the Fluxional Be6B11− and Chiral Be4B8 Clusters at Finite Temperatures Computed by DFT and Statistical Thermodynamics

    Density Functional Theory – Recent Advances, New Perspectives and Applications (IntechOpen) (2022)Chapter

    doi:10.5772/intechopen.100771

  • Cesar Castillo-Quevedo, Carlos Emiliano Buelna-Garcia, Edgar Paredes-Sotelo, Eduardo Robles-Chaparro, Edgar Zamora-Gonzalez, Martha Fabiola Martin-del-Campo-Solis, Jesus Manuel Quiroz-Castillo, Teresa del-Castillo-Castro, Gerardo Martínez-Guajardo, Aned de-Leon-Flores, Manuel Cortez-Valadez, Filiberto Ortiz-Chi, Tulio Gaxiola, Santos Jesus Castillo, Alejandro Vásquez-Espinal, Sudip Pan, Jose Luis Cabellos

    Effects of Temperature on Enantiomerization Energy and Distribution of Isomers in the Chiral Cu13 Cluster

    Molecules 26(18), 5710 (2021)

    doi:10.3390/molecules26185710

  • Carlos Emiliano Buelna-Garcia, Cesar Castillo-Quevedo, Jesus Manuel Quiroz-Castillo, Gerardo Martinez-Guajardo, Aned de-Leon-Flores, Gilberto Anzueto-Sanchez, Martha Fabiola Martin-del-Campo-Solis, Jose Luis Cabellos

    Effects of Temperature on IR Spectroscopy of the Fluxional Be6B11− Cluster

    Prime Archives in Material Science (2021)Chapter

    PDFdoi:10.37247/pams2ed.2.2021.25

  • 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

    Theoretical Prediction of Structures, Vibrational Circular Dichroism, and Infrared Spectra of Chiral Be4B8 Cluster at Different Temperatures

    Molecules 26(13), 3953 (2021)

    doi:10.3390/molecules26133953

  • Analila Luna-Valenzuela, José Luis Cabellos, Alvaro Posada-Amarillas

    Effect of temperature on the structure of Pd8 and Pd7Au1 clusters: an ab initio molecular dynamics approach

    Theoretical Chemistry Accounts 140(7) (2021)

    doi:10.1007/s00214-021-02771-8

  • Martha Fabiola Martin-del-Campo-Solis, Cesar Castillo-Quevedo, Edgar Zamora-Gonzalez, Carlos Emiliano Buelna-García, Eduardo Robles-Chaparro, Gerardo Martínez-Guajardo, Aned de-Leon-Flores, Gilberto Anzueto-Sánchez, Jose Luis Cabellos

    Exploration of Free Energy Surface of Chiral Be4B8 Cluster at Different Temperatures

    Prime Archives in Material Science (2021)Chapter

    doi:10.37247/pams2ed.3.2021.29

  • Carlos Emiliano 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

    Exploration of Free Energy Surface and Thermal Effects on Relative Population and Infrared Spectrum of the Be6B11− Fluxional Cluster

    Materials 14(1), 112 (2020)

    doi:10.3390/ma14010112

  • Said Jalife, Lei Liu, Sudip Pan, José Luis Cabellos, Edison Osorio, Cheng Lu, Thomas Heine, Kelling J. Donald, Gabriel Merino

    Dynamical behavior of boron clusters

    Nanoscale 8(40), 17639–17644 (2016)

    doi:10.1039/c6nr06383g

  • Gerardo Martínez-Guajardo, José Luis Cabellos, Andres Díaz-Celaya, Sudip Pan, Rafael Islas, Pratim K. Chattaraj, Thomas Heine, Gabriel Merino

    Dynamical behavior of Borospherene: A Nanobubble

    Scientific Reports 5, 11287 (2015)

    PDFdoi:10.1038/srep11287

See all publications

Other research areas

  • Cluster structure prediction

    Global-minimum searches on the potential energy surfaces of atomic and molecular clusters using evolutionary algorithms coupled to density functional theory.

  • Chemical bonding and aromaticity

    Design and analysis of species with unconventional bonding, such as planar hypercoordinate carbons, molecular stars and tubular boron motifs.