Rationale for mixing exact exchange with density functional approximations

1996/12/08 by John P. Perdew, Matthias Ernzerhof, Kieron Burke · 1 voice · 29 citations
Engineering · Physics and Astronomy · #Advanced Chemical Physics Studies #Molecular Junctions and Nanostructures #Spectroscopy and Quantum Chemical Studies

paper · doi:10.1063/1.472933

openalex publication_date 1996/12/08 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/31

Abstract

Density functional approximations for the exchange-correlation energy EDFAxc of an electronic system are often improved by admixing some exact exchange Ex: Exc≊EDFAxc+(1/n)(Ex−EDFAx). This procedure is justified when the error in EDFAxc arises from the λ=0 or exchange end of the coupling-constant integral ∫10 dλ EDFAxc,λ. We argue that the optimum integer n is approximately the lowest order of Görling–Levy perturbation theory which provides a realistic description of the coupling-constant dependence Exc,λ in the range 0≤λ≤1, whence n≊4 for atomization energies of typical molecules. We also propose a continuous generalization of n as an index of correlation strength, and a possible mixing of second-order perturbation theory with the generalized gradient approximation.

Citations

• Exchange and correlation in atoms, molecules, and solids by the spin-density-functional formalism
• Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
• Density-functional thermochemistry. III. The role of exact exchange
• Electronic structure of solids
• Self-Consistent Equations Including Exchange and Correlation Effects

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Discussions

• PBE0 vs. PBE1PBE, which one is it? Aron Cohen reminded me. J. Chem. Phys. 1996, 105, 9982 doi.org/10.1063/1.47... "MP4 gives atomization energies for the G1 set with 2.6 kcal/mol error with respect t [bsky, 3 points, 1 comments]

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