Work

Atomization Energy Calculations in 13‐Atom Alkali Metal Clusters: Is There an Appropriate Exchange‐Correlation Functional?

Year: 2025

Type: article

Abstract: ABSTRACT Density functional theory (DFT) is a treatment widely employed for exploring the electronic structure of atoms, molecules, solids, and complex systems. Despite its efficiency and popularity, the accuracy of DFT results is highly dependent on the choice of exchange–correlation (XC) functionals. This study evaluates several XC functionals for calculating atomization energies in 13‐atom homo‐ and heteronuclear alkali metal clusters (X 13 and YX 12 , with X, Y = Li, Na, K, Rb, and Cs), comparing these results with reference data obtained from fixed‐node Diffusion Monte Carlo (DMC) simulations. Our findings emphasize the critical role of the correlation functional in achieving more accurate results. Moreover, empirical dispersion corrections are shown to be quite important for these systems. Notably, PBE and PBE0 functionals with D3‐BJ dispersion seem particularly reliable for atomization energy calculations in these clusters.

Source: Journal of Computational Chemistry

DOI: 10.1002/jcc.70187

Authors: Wagner F. D. Angelotti, Lucila C. Z. Angelotti, Roberto L. A. Haiduke

Institutions: Universidade Federal do Triângulo Mineiro, Centro Universitário Barão de Mauá, Universidade de São Paulo, Instituto de Química de São Carlos

Language: English

Topic: Advanced Chemical Physics Studies

Subfield: Atomic and Molecular Physics, and Optics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,520

Funders: Fundação de Amparo à Pesquisa do Estado de São Paulo, Conselho Nacional de Desenvolvimento Científico e Tecnológico