Improving the Performance of Tao-Mo Non-empirical Density Functional with Broader Applicability in Quantum Chemistry and Materials Science.

A revised version of the semilocal exchange-correlation functional [Tao, J.; Mo, Y. Phys. Rev. Lett. 2016, 117, 073001] (TM) is proposed by incorporating the modifications to its correlation content obtained from the full high-density second-order gradient expansion as proposed in the case of the revised Tao-Perdew-Staroverov-Scuseria (revTPSS) [Perdew, J. P.; Ruzsinszky, A.; Csonka, G. I.; Constantin, L. A.; Sun, J. Phys. Rev. Lett. 2009, 103, 026403] functional. The present construction improves the performance of the TM functional over a wide range of quantum chemical and solid-state properties (thermochemical and structural). More specifically, the cohesive energies, jellium surface exchange-correlation energies, and real metallic surface energies are improved by preserving the accuracy of the solid-state lattice constants and bulk moduli. The present proposition is not only physically motivated but also enhances the applicability of the TM functional. New physical insights with the proper exemplification of the present modification, which is presented here, can further help in constructing more realistic non-empirical density functionals.