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.
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8 December 1996
Research Article|
December 08 1996
Rationale for mixing exact exchange with density functional approximations
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John P. Perdew;
John P. Perdew
Department of Physics and Quantum Theory Group, Tulane University, New Orleans, Louisiana 70118
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Matthias Ernzerhof;
Matthias Ernzerhof
Department of Physics and Quantum Theory Group, Tulane University, New Orleans, Louisiana 70118
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Kieron Burke
Kieron Burke
Department of Chemistry, Rutgers University, Camden, New Jersey 08102
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John P. Perdew
Matthias Ernzerhof
Kieron Burke
Department of Physics and Quantum Theory Group, Tulane University, New Orleans, Louisiana 70118
J. Chem. Phys. 105, 9982–9985 (1996)
Article history
Received:
June 11 1996
Accepted:
September 05 1996
Citation
John P. Perdew, Matthias Ernzerhof, Kieron Burke; Rationale for mixing exact exchange with density functional approximations. J. Chem. Phys. 8 December 1996; 105 (22): 9982–9985. https://doi.org/10.1063/1.472933
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