An assessment of theoretical methods for nonbonded interactions: comparison to complete basis set limit coupled-cluster potential energy curves for the benzene dimer, the methane dimer, benzene-methane, and benzene-H2S.
Large, correlation-consistent basis sets have been used to very closely approximate the coupled-cluster singles, doubles, and perturbative triples [CCSD(T)] complete basis set potential energy curves of several prototype nonbonded complexes, the sandwich, T-shaped, and parallel-displaced benzene dimers, the methane-benzene complex, the H2S-benzene complex, and the methane dimer. These benchmark potential energy curves are used to assess the performance of several methods for nonbonded interactions, including various spin-component-scaled second-order perturbation theory (SCS-MP2) methods, the spin-component-scaled coupled-cluster singles and doubles method (SCS-CCSD), density functional theory empirically corrected for dispersion (DFT-D), and the meta-generalized-gradient approximation functionals M05-2X and M06-2X. These approaches generally provide good results for the test set, with the SCS methods being somewhat more robust. M05-2X underbinds for the test cases considered, while the performances of DFT-D and M06-2X are similar. Density fitting, dual basis, and local correlation approximations all introduce only small errors in the interaction energies but can speed up the computations significantly, particulary when used in combination.
Sherrill
C David
CD
Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia, 30332-0400, USA. sherrill@gatech.edu
Takatani
Tait
T
Hohenstein
Edward G
EG
D001554:Benzene / Q000737:chemistry*; D003198:Computer Simulation; D019281:Dimerization; D006862:Hydrogen Sulfide / Q000737:chemistry*; D008697:Methane / Q000737:chemistry*; D008956:Models, Chemical; D011789:Quantum Theory
D001554:Benzene; D008697:Methane; D006862:Hydrogen Sulfide