Abstract
A comprehensive study is undertaken to assess the nonempirical meta-generalized gradient approximation (MGGA) of Tao, Perdew, Staroverov, and Scuseria (TPSS) against 14 common exchange-correlation energy functionals. Principal results are presented in the form of statistical summaries of deviations from experiment for the G3/99 test set (223 enthalpies of formation, 86 ionization potentials, 58 electron affinities, 8 proton affinities) and three additional test sets involving 96 bond lengths, 82 harmonic vibrational frequencies, and 10 hydrogen-bonded complexes, all computed using the 6-311++G(3df,3pd) basis. The TPSS functional matches, or exceeds in accuracy all prior nonempirical constructions and, unlike semiempirical functionals, consistently provides a high-quality description of diverse systems and properties. The computational cost of self-consistent MGGA is comparable to that of ordinary GGA, and exact exchange (unavailable in some codes) is not required. A one-parameter global hybrid version of the TPSS functional is introduced and shown to give further improvement for most properties.
Keywords
Electron affinity (data page)Density functional theoryAffinitiesHybrid functionalBasis setMoleculeComputational chemistryHydrogen bondStandard enthalpy of formationHarmonicIonizationIonization energyBasis (linear algebra)ChemistrySet (abstract data type)MathematicsPhysicsPhysical chemistryQuantum mechanicsComputer scienceStereochemistryGeometryOrganic chemistry
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Publication Info
- Year
- 2003
- Type
- article
- Volume
- 119
- Issue
- 23
- Pages
- 12129-12137
- Citations
- 2660
- Access
- Closed
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Cite This
Viktor N. Staroverov,
Gustavo E. Scuseria,
Jianmin Tao
et al.
(2003).
Comparative assessment of a new nonempirical density functional: Molecules and hydrogen-bonded complexes.
The Journal of Chemical Physics
, 119
(23)
, 12129-12137.
https://doi.org/10.1063/1.1626543
Identifiers
- DOI
- 10.1063/1.1626543