Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation

John P. Perdew, J. A. Chevary, S. H. Vosko, Koblar A. Jackson, Mark R. Pederson, D. J. Singh, and Carlos Fiolhais
Phys. Rev. B 46, 6671 – Published 15 September 1992; Erratum Phys. Rev. B 48, 4978 (1993)
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Abstract

Generalized gradient approximations (GGA’s) seek to improve upon the accuracy of the local-spin-density (LSD) approximation in electronic-structure calculations. Perdew and Wang have developed a GGA based on real-space cutoff of the spurious long-range components of the second-order gradient expansion for the exchange-correlation hole. We have found that this density functional performs well in numerical tests for a variety of systems: (1) Total energies of 30 atoms are highly accurate. (2) Ionization energies and electron affinities are improved in a statistical sense, although significant interconfigurational and interterm errors remain. (3) Accurate atomization energies are found for seven hydrocarbon molecules, with a rms error per bond of 0.1 eV, compared with 0.7 eV for the LSD approximation and 2.4 eV for the Hartree-Fock approximation. (4) For atoms and molecules, there is a cancellation of error between density functionals for exchange and correlation, which is most striking whenever the Hartree-Fock result is furthest from experiment. (5) The surprising LSD underestimation of the lattice constants of Li and Na by 3–4 % is corrected, and the magnetic ground state of solid Fe is restored. (6) The work function, surface energy (neglecting the long-range contribution), and curvature energy of a metallic surface are all slightly reduced in comparison with LSD. Taking account of the positive long-range contribution, we find surface and curvature energies in good agreement with experimental or exact values. Finally, a way is found to visualize and understand the nonlocality of exchange and correlation, its origins, and its physical effects.

  • Received 10 December 1991

DOI:https://doi.org/10.1103/PhysRevB.46.6671

©1992 American Physical Society

Erratum

Erratum: Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation

John P. Perdew, J. A. Chevary, S. H. Vosko, Koblar A. Jackson, Mark R. Pederson, D. J. Singh, and Carlos Fiolhais
Phys. Rev. B 48, 4978 (1993)

Authors & Affiliations

John P. Perdew

  • Department of Physics and Quantum Theory Group, Tulane University, New Orleans, Louisiana 70118

J. A. Chevary and S. H. Vosko

  • Department of Physics, University of Toronto, Toronto, Ontario, Canada M5S 1A7

Koblar A. Jackson, Mark R. Pederson, and D. J. Singh

  • Complex Systems Theory Branch, Naval Research Laboratory, Washington, D.C. 20375-5000

Carlos Fiolhais

  • Department of Physics, University of Coimbra, 3000 Coimbra, Portugal

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Vol. 46, Iss. 11 — 15 September 1992

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