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Physics and Chemistry of Minerals, 2014, Volume 41, Issue 1, pp 17-25.
G. V. Gibbs (1) (2) (3), N. L. Ross (1), D. F. Cox (4), K. M. Rosso (5), B. B. Iversen (6), M. A. Spackman (7)
The power law regression equation, = 1.46(r c)>/r)−0.19, relating the average experimental bond lengths, , to the average accumulation of the electron density at the bond critical point, r c)>, between bonded pairs of metal and oxygen atoms (r is the row number of the M atom), determined at ambient conditions for oxide crystals, is similar to the regression equation R(M–O) = 1.41(ρ(r c)/r)−0.21 determined for three perovskite crystals at pressures as high as 80 GPa. The pair are also comparable with the equation = 1.43(/r)−0.21 determined for oxide crystals at ambient conditions and = 1.39(/r)−0.22 determined for geometry-optimized hydroxyacid molecules that relate the geometry-optimized bond lengths to the average Pauling bond strength, , for the M–O bonded interactions. On the basis of the correspondence between the equations relating r c)> and with bond length, it seems plausible that the Pauling bond strength might serve a rough estimate of the accumulation of the electron density between M–O bonded pairs of atoms. Similar expressions, relating bond length and bond strength hold for fluoride, nitride and sulfide molecules and crystals. The similarity of the expressions for the crystals and molecules is compelling evidence that molecular and crystalline M–O bonded interactions are intrinsically related. The value of r c)> = r[(1.41)/]4.76 determined for the average bond length for a given coordination polyhedron closely matches the Pauling’s electrostatic bond strength reaching each the coordinating anions of the coordinated polyhedron. Despite the relative simplicity of the expression, it appears to be more general in its application in that it holds for the bulk of the M–O bonded pairs of atoms of the periodic table.
