Role of Exact Exchange and Empirical Dispersion in Density Functional Theory-Based Three-Body Noncovalent Interactions

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.