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    8 views5 pages

    LYP PRB 1988 37 785

    Uploaded by

    chama_goz
    LYP_prb_1988_37_785

    Copyright:

    © All Rights Reserved
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    PHYSICAL REVIEW B VOLUME 37, NUMBER 2 1S JANUARY 1988-1 Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Chengteh Lee, Weitao Yang, and Robert G. Parr Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27514 (Received 20 May 1987; revised manuscript received 27 August 1987) A correlation-energy formula due to Colle and Salveti (Theor. Chim. Acta 37, 329 (1975), in Which the correlation energy density is expressed in terms ofthe electron density and a Laplacian of the second-order Hartree-Fock density matrix, is restated as a formula involving the density land Idcal 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, itis demonstrated that these formulas, like the original Colle- Salvetti formulas, give correlation energies within a ew percent 1. INTRODUCTION Interest in calculation of the correlation energy continues unabated.'? We here report a new development, in Which the Colle-Salvetti formula for calculating correlation energy from the Hartree-Fock second-order density ma- trix’ is converted into a density-functional formula. Let pir) be the Hartree-Fock electron density and p!!"(r;,r;) be the diagonal element of the second-order Hartree- Fock reduced density matrix, MWD p, elcury J ivr no )[2doydoy ++ doydeytey “dry o 2 pcan also be expressed in terms of interparticle coordinates, p!¥(r,8), where nth 2 ‘The Colle-Salvetti formula for correlation energy then is Le bptr)"19%oE ati) +bple- (3p T+dptr y Sarr @ esr) pir where a =0.049 18, 6 =0.132, ¢ =0.2533, and d =0.349, This formula was arrived at by Colle and Salvetti by a theoretical analysis accompanied by a series of approxi- ‘mations, beginning (essentially) from the reasonable pro- position that the second-order density matrix including correlation may approximated by the Hartree-Fock second-order density matrix times a correlation factor. ‘The constants a, 6, c, and d in the final formula were ob- tained by a fitting procedure using only the Hartree Fock orbital for the helium atom. Colle and Salvetti demonstrated that Eq. (3) gave good predicted correl tion energies for atoms and molecules.” They also pro- vided and tested a generalized form for open-shell sys- tems. Here we carry on the analysis of Eq. (3) itself. Il, FORMULAS INVOLVING LOCAL. KINETIC-ENERGY DENSITIES First consider a closed-shell atom or molecule, having an even number of electrons. Then piers r3) where pi™ is the Hartree-Fock first-order reduced densi- ty matrix, wf pre e SY ini) WF ro p03 ++) xdoydoy dnd, 0 Note that piFte,e)=ple) and piFir,r)=4p%(e). In the interparticle coordinates of Eq, (2), (4) reads pies)=$ple-+s/2)ptr—s/2) Heirs 2,2-82)F , o and there follows Ts ©1988 The American Physical Society 786 (Vip! x81], Gxlp)=Fiipp*e-""? V, DISCUSSION 26) F 5 (or G4) is the first derivative of F, (or Gz) with respect to par). The zero-order formulas for the correla- tion potential are obtained by omitting the last bracket- ‘The Colle-Salvetti correlation energy formula, in the

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