Data-Driven Improvement of Local Hybrid Functionals: Neural-Network-Based Local Mixing Functions and Power-Series Correlation Functionals.

Abstract

Local hybrid functionals (LHs) use a real-space position-dependent admixture of exact exchange (EXX), governed by a local mixing function (LMF). The systematic construction of LMFs has been hampered over the years by a lack of exact physical constraints on their valence behavior. Here, we exploit a data-driven approach and train a new type of "n-LMF" as a relatively shallow neural network. The input features are of meta-GGA character, while the W4-17 atomization-energy and BH76 reaction-barrier test sets have been used for training. Simply replacing the widely used "t-LMF" of the LH20t functional by the n-LMF provides the LH24n-B95 functional. Augmented by DFT-D4 dispersion corrections, LH24n-B95-D4 remarkably improves the WTMAD-2 value for the large GMTKN55 test suite of general main-group thermochemistry, kinetics, and noncovalent interactions (NCIs) from 4.55 to 3.49 kcal/mol. As we found the limited flexibility of the B95c correlation functional to disfavor much further improvement on NCIs, we proceeded to replace it by an optimized B97c-type power-series expansion. This gives the LH24n functional. LH24n-D4 gives a WTMAD-2 value of 3.10 kcal/mol, the so far lowest value of a rung 4 functional in self-consistent calculations. The new functionals perform moderately well for organometallic transition-metal energetics while leaving room for further data-driven improvements in that area. Compared to complete neural-network functionals like DM21, the present more tailored approach to train just the LMF in a flexible but well-defined human-designed LH functional retains the possibility of graphical LMF analyses to gain deeper understanding. We find that both the present n-LMF and the recent x-LMF suppress the so-called gauge problem of local hybrids without adding a calibration function as required for other LMFs. LMF plots show that this can be traced back to large LMF values in the small-density region between the interacting atoms in NCIs for n- and x-LMFs and low values for the t-LMF. We also find that the trained n-LMF has relatively large values in covalent bonds without deteriorating binding energies. The current approach enables fast and efficient routine self-consistent calculations using n-LMFs in Turbomole.