Performance of meta-GGA functionals on general main group thermochemistry, kinetics, and noncovalent interactions

Pan Hao, Jianwei Sun, Bing Xiao, Adrienn Ruzsinszky, Gábor I. Csonka, Jianmin Tao, Stephen Glindmeyer, John P. Perdew

Research output: Contribution to journalArticle

46 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)355-363
Number of pages9
JournalJournal of chemical theory and computation
Volume9
Issue number1
DOIs
Publication statusPublished - Jan 8 2013

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

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