Surprisingly Good Performance of XYG3 Family Functionals Using 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 wavefunction ab initio approaches. Intriguingly: (a) the introduction of E3 makes an empirical dispersion correction redundant; (b) GGA or mGGA semilocal correlation functionals offer no advantage over 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 6-parameter functional with WTMAD2=1.42 that has no post-LDA DFT components and no dispersion correction in the final energy.

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• Explicitly correlated double hybrid DFT: a comprehensive analysis of the basis set convergence on the GMTKN55 database
• A double-hybrid density functional based on good local physics with outstanding performance on the GMTKN55 database
• Does GLPT2 Offer Any Actual Benefit Over Conventional HF-MP2 In the Context of Double-Hybrid Density Functionals?
• WTMAD-4: A Fair Weighting Scheme for GMTKN55