Assessment of advanced xDH@B3LYP methods in describing various potential energy curves driven by π-π, CH/π, and SH/π non-bonded interactions

Abstract

Accurate description of potential energy curves driven by non-bonded interactions remains a great challenge for pure density functional approximations (DFAs). It is because the R−6 decay behavior of dispersion cannot be intrinsically captured by the (semi)-local ingredients and the exact-exchange used in the popular hybrid DFAs. Overemphasizing the accuracy on the equilibrium region for the functional construction would likely deteriorate the overall performance on the other regions of potential energy surfaces. In consequence, the empirical dispersion correction becomes the standard component in DFAs to treat the non-bonded interactions. In this Letter, we demonstrate that without the use of empirical dispersion correction, doubly hybrid approximations, in particular two recently proposed revXYG3 and XYG7 functionals, hold the promise to have a balanced description of non-bonded interactions on the whole potential energy curves for several prototypes of π- π, CH/ π, and SH/ π interactions. The error of revXYG3 and XYG7 for non-bonded interactions is around 0.1 kcal/mol, and their potential energy curves almost coincide with the accurate CCSD(T)/CBS curves.