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

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

Research output: Contribution to journalArticle

41 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

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Thermochemistry
thermochemistry
functionals
gradients
Kinetics
kinetics
approximation
set theory
interactions
range errors
Diels-Alder reactions
comfort
energy
rings

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications

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Performance of meta-GGA functionals on general main group thermochemistry, kinetics, and noncovalent interactions. / Hao, Pan; Sun, Jianwei; Xiao, Bing; Ruzsinszky, Adrienn; Csonka, G.; Tao, Jianmin; Glindmeyer, Stephen; Perdew, John P.

In: Journal of Chemical Theory and Computation, Vol. 9, No. 1, 08.01.2013, p. 355-363.

Research output: Contribution to journalArticle

Hao, Pan ; Sun, Jianwei ; Xiao, Bing ; Ruzsinszky, Adrienn ; Csonka, G. ; Tao, Jianmin ; Glindmeyer, Stephen ; Perdew, John P. / Performance of meta-GGA functionals on general main group thermochemistry, kinetics, and noncovalent interactions. In: Journal of Chemical Theory and Computation. 2013 ; Vol. 9, No. 1. pp. 355-363.
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