Assessing Computational Methods to Calculate the Binding Energies of Dimers of Five-Membered Heterocyclic Molecules

Abstract

Computational electronic structure methods, including ab initio and density functional theory (DFT), have been assessed in calculating the binding energies of 14 five-membered heterocyclic dimers. The configurations were generated using classical molecular dynamics before optimization at the MP2/aug-cc-pVTZ. Benchmark binding energies are calculated at the CCSD(T)/CBS level of theory. Among the ab initio methods, the DLPNO-CCSD(T)/CBS method has the best performance, reproducing CCSD(T)/CBS with a mean absolute deviation (MAD) of 0.17 kcal/mol. In addition, a schematic CCSD(T)/CBS approach perfectly reproduces the canonical CCSD(T)/CBS with a mean absolute error of 0.08 kcal/mol. Regarding DFT functionals, it has been found that counterpoise corrections have negligible effects on the accuracy of the functionals. Furthermore, including the D3 empirical dispersion considerably enhances the accuracy of the DFT functionals. As a result, outstanding performance is noted for the double hybrid functional B2K-PLYP, with a mean absolute error of 0.25 kcal/mol. In addition to the B2K-PLYP double hybrid functional, M05-D3, B97D, M05-2X-D3, M05-2X, M06-HF, M08-HX, M11, TPSSh-D3, and RSX-0DH-D3(BJ) have MAD values lower than 0.5 kcal/mol. These functionals are recommended for further investigations of five-membered heterocyclic clusters.