Reworking the Tao-Mo Exchange-Correlation Functional. III. Improved Deorbitalization Strategy and Faithful Deorbitalization.

Abstract

We present a deorbitalization of the recent simplified, regularized Tao-Mo exchange functional ( J. Chem. Phys. 2023, 159, 214102) that is faithful to the parent functional. That is a major gain relative to our earlier deorbitalization which did poorly on molecular heats of formation ( J. Chem. Phys. 2023, 159, 214103). The improvement arises from augmentation of the Mejía-Rodríguez and Trickey deorbitalization strategy ( Phys. Rev. A 2017, 96, 052512) to use a smoothed replacement for the reduced density Laplacian (conventionally denoted q) obtained from that Laplacian itself. The augmentation also rationalizes the improvement obtained from the cutoff of q < 0 that was poorly understood at the time of the previous paper. The new scheme yields deorbitalized chemical region indicators that are much closer to those from the parent, orbital-dependent functional than were obtainable from the previous deorbitalization. It also replicates the good 3d elemental magnetization of the parent functional reasonably well.