The role of exact exchange and empirical dispersion in Density Functional Theory-based three-body non-covalent interactions

Cafiero, M. ORCID: https://orcid.org/0000-0002-4895-1783 (2024) The role of exact exchange and empirical dispersion in Density Functional Theory-based three-body non-covalent interactions. Journal of Physical Chemistry A, 128 (40). pp. 8777-8786. ISSN 1520-5215 doi: 10.1021/acs.jpca.4c03262

Abstract/Summary

Total and three-body interaction energies are calculated for a benchmark set of three-body systems using a range of different types of density functional theory (DFT) methods, with the results compared to CCSD(T)/CBS results from the benchmark reference [Phys. Chem. Chem. Phys. 2023, 25, 28621–28637]. Inclusion of Hartree-Fock exchange, via either a global or range-separated hybrid approach or inclusion of empirical dispersion corrections, increases accuracy for total and three-body interactions. Basis set convergence testing shows that the aug-cc-pVTZ basis set is well converged with little to no change seen when using quadruple-ζ basis sets. The accuracy of the DFT methods is similar when calculating interaction energies for both global and local minimum structures. Overall, the CAM-B3LYP-D3BJ, B97D3, and ωB97XD functionals are recommended for calculating three-body interactions.

Item Type	Article
URI	https://reading-clone.eprints-hosting.org/id/eprint/118475
Identification Number/DOI	10.1021/acs.jpca.4c03262
Refereed	Yes
Divisions	Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
Publisher	American Chemical Society
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