Performance of meta-GGA
Functionals on General Main
Group Thermochemistry, Kinetics, and Noncovalent Interactions
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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<sup>–1</sup> (MGGA_MS) to 15 kcal mol<sup>–1</sup> (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