One-parameter optimization of a nonempirical meta-generalized-gradient-approximation for the exchange-correlation energy

John P. Perdew, Adrienn Ruzsinszky, Jianmin Tao, Gábor I. Csonka, and Gustavo E. Scuseria
Phys. Rev. A 76, 042506 – Published 9 October 2007

Abstract

The meta-generalized-gradient-approximation (meta-GGA) for the exchange-correlation energy, as constructed by Tao, Perdew, Staroverov, and Scuseria (TPSS) [Phys. Rev. Lett. 91, 146401 (2003)], has achieved usefully consistent accuracy for diverse systems and is the most reliable nonempirical density functional (and the most reliable nonhybrid) in common use. We present here an optimized version of this TPSS functional obtained by empirically fitting a single free parameter that controls the approach of the exchange enhancement factor to its rapidly-varying-density limit, while preserving all the exact constraints that the original TPSS functional satisfies. We find that molecular atomization energies are significantly improved with the optimized version and are even better than those obtained with the best hybrid functionals employing a fraction of exact exchange (e.g., the TPSS hybrid), while energy barrier heights are slightly improved; jellium surface energies remain accurate and almost unchanged. The one-parameter freedom of the TPSS functional may be useful even beyond the meta-GGA level, since the TPSS approximation is a natural starting point for the higher-level hyper-GGA.

  • Figure
  • Received 1 June 2007

DOI:https://doi.org/10.1103/PhysRevA.76.042506

©2007 American Physical Society

Authors & Affiliations

John P. Perdew1, Adrienn Ruzsinszky1, Jianmin Tao2, Gábor I. Csonka3, and Gustavo E. Scuseria4

  • 1Department of Physics and Quantum Theory Group, Tulane University, New Orleans, Louisiana 70118, USA
  • 2Department of Physics, University of Missouri–Columbia, Columbia, Missouri 65211, USA
  • 3Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, H-1521 Budapest, Hungary
  • 4Department of Chemistry, Rice University, Houston, Texas 77005, USA

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Vol. 76, Iss. 4 — October 2007

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