Density difference representation of electron correlation

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Abstract
The density difference ΔD (r1), defined as the difference between the exact radial density function Dex(r1), or our best approximation to it, and the best uncorrelated, that is, the Hartree–Fock, radial density function DHF(r1), is reported for the He, Li, and Be isoelectronic sequences and to a lesser accuracy for the carbon atom. By means of an analysis of the Be density difference in terms of K and L shell contributions some insight is gained for the evolution of the density difference through the He, Li, and Be sequence. In general the effect of electron correlation on the radial density function D (r1) and, of course, on the related density distribution ρ (r1) diminishes as the charge cloud becomes less diffuse. The effect of electron correlation on one‐electron distributions is also demonstrated by comparison of 〈rn1〉 expectation values. Analytical Hartree–Fock wavefunctions are reported for H− (energy =−0.4879 2973 a.u.) and Li− (energy =−7.428 2317 a.u.).

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