Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
Развитие формулы корреляционной энергии Колле–Сальветти в функционал от плотности электронов
1988-01-15
SCID: 54.1/gyf86hha
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Colle-Salvetti correlation-energy formulacorrelation energy densityelectron densitygradient expansionlocal kinetic-energy density
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Abstract (AI)
A correlation-energy formula due to Colle and Salvetti [Theor. Chim. Acta 37, 329 (1975)], in which the correlation energy density is expressed in terms of the electron density and a Laplacian of the second-order Hartree-Fock density matrix, is restated as a formula involving the density and local kinetic-energy density. On insertion of gradient expansions for the local kinetic-energy density, density-functional formulas for the correlation energy and correlation potential are then obtained. Through numerical calculations on a number of atoms, positive ions, and molecules, of both open- and closed-shell type, it is demonstrated that these formulas, like the original Colle-Salvetti formulas, give correlation energies within a few percent.
Key Findings
1
By inserting gradient expansions for the local kinetic-energy density, density-functional formulas for both the correlation energy and the correlation potential are derived.
2
Numerical calculations on various atoms, positive ions, and molecules (open- and closed-shell) show the derived formulas reproduce correlation energies within a few percent, similar to the original Colle–Salvetti results.
3
The Colle–Salvetti correlation-energy formula, originally using electron density and the Laplacian of the second-order HF density matrix, is reformulated as a functional of the electron density and local kinetic-energy density.
Research Object
Colle–Salvetti correlation-energy formula developed into a density functional (correlation-energy functional of the electron density and local kinetic-energy density)
Research Subject
Derivation and assessment of density-functional correlation energy and correlation potential expressions (using local kinetic-energy density and gradient expansions) and their numerical accuracy for atoms, positive ions, and molecules
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1988-01-15
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