Performance of meta-GGA Functionals on General Main Group Thermochemistry, Kinetics, and Noncovalent Interactions.

Abstract

Among the computationally efficient semilocal density functionals for the exchange-correlation energy, meta-generalized-gradient approximations (meta-GGAs) are potentially the most accurate. Here, we assess the performance of three new meta-GGAs (revised Tao-Perdew-Staroverov-Scuseria or revTPSS, regularized revTPSS or regTPSS, and meta-GGA made simple or MGGA_MS), within and beyond their "comfort zones," on Grimme's big test set of main-group molecular energetics (thermochemistry, kinetics, and noncovalent interactions). We compare them against the standard Perdew-Burke-Ernzerhof (PBE) GGA, TPSS, and Minnesota M06L meta-GGAs, and Becke-3-Lee-Yang-Parr (B3LYP) hybrid of GGA with exact exchange. The overall performance of these three new meta-GGA functionals is similar. However, dramatic differences occur for different test sets. For example, M06L and MGGA_MS perform best for the test sets that contain noncovalent interactions. For the 14 Diels-Alder reaction energies in the "difficult" DARC subset, the mean absolute error ranges from 3 kcal mol(-1) (MGGA_MS) to 15 kcal mol(-1) (B3LYP), while for some other reaction subsets the order of accuracy is reversed; more generally, the tested new semilocal functionals outperform the standard B3LYP for ring reactions. Some overall improvement is found from long-range dispersion corrections for revTPSS and regTPSS but not for MGGA_MS. Formal and universality criteria for the functionals are also discussed.