Benchmark of density functional theory methods on the prediction of bond energies and bond distances of noble-gas containing molecules

We have tested three pure density functional theory (DFT) functionals, BLYP, MPWPW91, MPWB95, and ten hybrid DFT functionals, B3LYP, B3P86, B98, MPW1B95, MPW1PW91, BMK, M05-2X, M06-2X, B2GP-PLYP, and DSD-BLYP with a series of commonly used basis sets on the performance of predicting the bond energies and bond distances of 31 small neutral noble-gas containing molecules. The reference structures were obtained using the CCSD(T)/aug-cc-pVTZ theory and the reference energies were based on the calculation at the CCSD(T)/CBS level. While in general the hybrid functionals performed significantly better than the pure functionals, our tests showed a range of performance by these hybrid functionals. For the bond energies, the MPW1B95/6-311+G(2df,2pd), BMK/aug-cc-pVTZ, B2GP-PLYP/aug-cc-pVTZ, and DSD-BLYP/aug-cc-pVTZ methods stood out with mean unsigned errors of 2.0-2.3 kcal/mol per molecule. For the bond distances, the MPW1B95/6-311+G(2df, 2pd), MPW1PW91/6-311+G(2df,2pd), and B3P86/6-311+G(2df,2pd), DSD-BLYP/6-311+G(2df,2pd), and DSD-BLYP/aug-cc-pVTZ methods stood out with mean unsigned errors of 0.008-0.013 angstrom per bond. The current study showed that a careful selection of DFT functionals is very important in the study of noble-gas chemistry, and the most recommended methods are MPW1B95/6-311+G(2df, 2pd) and DSD-BLYP/aug-cc-pVTZ. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3603455]