Surprisingly Good Performance of XYG3 Family Functionals Using a Scaled KS-MP3 Correlation

Abstract

By adding a GLPT3 (third-order Görling-Levy perturbation theory, or KS-MP3) term E3 to the XYG7 form for a double hybrid, we are able to bring down WTMAD2 (weighted total mean absolute deviation) for the very large and chemically diverse GMTKN55 benchmark to an unprecedented 1.17 kcal/mol, competitive with much costlier composite wave function ab initio approaches. Intriguingly, (a) the introduction of E3 makes an empirical dispersion correction redundant; (b) generalized gradient approximation (GGA) or meta-GGA semilocal correlation functionals offer no advantage over the local density approximation (LDA) in this framework; (c) if a dispersion correction is retained, then simple Slater exchange leads to no significant loss in accuracy. It is possible to create a six-parameter functional with WTMAD2 = 1.42 that has no post-LDA density functional theory components and no dispersion correction in the final energy.