The aim was to investigate the relationship between the bond length and the electron density at the bond critical point in homonuclear X--X and Z--Z and heteronuclear C--Z bonds (X = Li-F, Z = Na-Cl). The d,rho(c) pairs were obtained from 472 target bonds in DFT-optimized (B3LYP/6-311+G(d,p)) small molecular species. These species were selected arbitrarily but with a view to maximize the range widths WR for each atom combination. It was found that (i) with one clear exception, the d(A - A) means (A = X or Z) correlate linearly with the bond lengths d(A(2)) of the respective diatomic molecules; (ii) the d(A - A) means correlate parabolically with n, the formal number of valence electrons in the atoms of the bond; and (iii) with increasing sample size N the ratio WR(rho(c))/WR(d) appears to converge toward a representation f [WR(rho(c))/WR(d)](N-->infinity) characteristic of A. Detailed analysis of the d,rho(c) relationship has shown that by and large simple power regression accounts best for the DFT data. The regression coefficients of d = arho(c) (-b) and rho(c) = alphad(-beta) (b, beta > 0) vary with n in a seemingly irregular manner but one that is consistent with simple chemical notions. The d(A(2)) can be approximated in terms of multilinear MO electron occupancies.
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