Towards chemical accuracy for the thermodynamics of large molecules: new hybrid density functionals including non-local correlation effects

Abstract

Two hybrid density functionals that include a second-order perturbation correction for non-local correlation effects are tested for the full G3/05 test set. Very large AO basis sets including core-polarization/correlation functions have been employed that yield for the first time results quite close to the basis set limit for this set. The B2-PLYP functional and the new mPW2-PLYP approach with a modified exchange part give by far the lowest MAD over the whole G3/05 set ever reported for a DFT method (2.5 and 2.1 kcal mol⁻¹, respectively). The big improvement compared to common density functionals is further demonstrated by the reduction of the maximum and minimum errors (outliers) and by much smaller errors for complicated molecular systems.