Electron transfer spectra of hexahalide complexes

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Abstract
The electron transfer spectra of the chloro, bromo, and iodo complexes of Ru(III), Ru(IV), Rh(III), Pd(IV), Sn(IV), Sb(V), W(VI), Re(IV), Os(III), Os(IV), Ir(III), Ir(IV), Pt(IV), and Pb(IV) are studied and interpreted by group-theoretical methods as transitions of π (and at higher wave-numbers, σ) electrons, mainly localized in the ligands, to the available orbitals of even parity γ 5, γ 3 and γ 1, representing mainly d, d, and s electrons of the central ion. The half-widths and intensities of the bands support the identification. The remarkable similarity between the spectra of d 4 and d 5 systems with the same set of ligands is explained by the presence of only one effective excited state of the central ion. The structure expected of the group of π transfer bands as function of increasing Landé parameter ζ np of the halogen is calculated. The use of pure molecular orbital (M.O.) configurations as a convenient classification (but not a very good approximation to the wave-function) is compared to the analogous case of atomic spectroscopy. It is recommended to estimate the M.O. energies from absorption spectra rather than to try to calculate them from unreliable approximations.