A performance study of density functional theory with empirical dispersion corrections and spin-component scaled second-order Møller−Plesset perturbation theory on adsorbate–zeolite interactions

Abstract

Density functional theory models, PBE, BLYP, B3LYP, B2PLYP and mPW2PLYP, with empirical dispersion corrections and the spin-component scaled second-order Møller−Plesset perturbation theory, SCS-MP2, were tested against the benchmarking adsorbate–zeolite models of Zhao and Truhlar. The van der Waals dispersion correction improves the binding energy significantly for all considered exchange–correlation functionals. The adsorption energies from the density functional theory with double perturbation correction with dispersion term, B2PLYP-D and mPW2PLYP-D, match the CCSD(T) results extrapolated to the complete-basis set even better. The mean unsigned errors of counterpoise-corrected binding energy of B2PLYP-D and mPW2PLYP-D methods are only 0.17 and 0.08 kcal/mol, respectively. The double-hybrid density functional with dispersion corrections should be used for high accuracy zeolite computation. Alternatively, the counterpoise-uncorrected SCS-MP2 calculation can be used to estimate the binding energy due to some cancellation of errors. Finally, an importance of the speed-up algorithms such as RI-MP2, RIJCOSX and RI-J, for the methods considered in this work was demonstrated by using 3T and 16T zeolite cluster models.