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Reparametrization of the Colle-Salvetti formula
Adam L Baskerville1, Msugh Targema1, Hazel Cox1
1Department of Chemistry, School of Life Sciences, University of Sussex, Falmer, Brighton BN1 9QJ, UK.
Abstract:
We investigate the Colle-Salvetti (CS) formula, the basis of the Lee, Yang and Parr (LYP) correlation functional used in approximate density functional theory. The CS formula is reparametrized using high-accuracy Hartree-Fock (HF) wavefunctions to determine the accuracy of the formula to calculate anions. Fitting to the hydride ion or the two-electron system just prior to electron detachment at the HF level of theory does not, in general, improve the calculated correlation energies using the parameters derived from the CS/LYP method. An analysis of the CS parameters used in the popular LYP functional demonstrates the ingenuity and perhaps fortuitousness of the original formulation by CS.
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