Electronic Structure and Stability of Hydrogen Halides and of Complex Ions XO4

Abstract

(1) It is shown that in the hydrogen halide molecules (internuclear distance r0) the proton penetrates the electronic shell of the anion to a depth which for the simplified case of spherical symmetry can be characterized by the condition: The amount of negative charge beyond the sphere of radius r0 equals −1e. (2) From the dipole moments μ=xer0 of the hydrogen halide molecules it can be concluded: The wave mechanical distribution of the negative charge of the free halide ions is changed by the introduction of the proton in such a way that the center of gravity of an amount of charge equal to —(1−x)e is shifted from the halogen nucleus to the proton. The fraction (1—x) increases with the electronic polarizability of the anion, and would be equal to 1 for an ion of infinitely large polarizability, leading to a completely unpolar type of binding in this case. (3) It is shown that for the complex ions SiO44—, PO43—, SO4=, and ClO4−, the gradation of the X☒O distances and of the molar dispersion can be easily understood from the point of view used in 1924 for the case of the molar refraction: These ions represent the result of the polarization of O= by Si4+, P5+, S6+, and Cl7+, and the X☒O binding in them shows gradual changes toward the unpolar type. (4) It is pointed out that the relatively unstable HI and ClO4− approach the unpolar type of binding more closely than any other of the compounds considered here. The generalization of this connection between instability and the degree of deformation of electronic shells explains why compounds like FO4− and BrO4− are unknown.