On the Ultraviolet Absorption Spectra of Uninegative Ions

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Abstract
New spectral data are reported for NO2−, ClO2−, and ClO− in aqueous solution. The theory of the electron transfer spectra of aqueous halide ions is extended to uninegative polyatomic ions by allowing for the greater excitation energy of the polyatomic radicals produced in the act of absorption, as compared with the excitation energy of the atoms produced from halide ions. This additional excitation energy arises from the operation of the Franck‐Condon principle in determining the internuclear distances in the radical. Tri‐iodide ion is the only one of the uninegative ions for which the required data are available and for which these data are not consistent with the assignment of the intense ultraviolet bands to transitions involving transfer of an electron to the solvent. It is found that the low intensity absorption bands of NO2− and ClO2− coincide with the bands predicted by R. S. Mulliken for triatomic oxide molecules (AO2), with the same numbers of valence electrons.

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