The Spectra and Photochemistry of Inorganic Anions

摘要

The photoionization of N3(-) in aqueous solutions was investigated by methods of steady photochemistry and flash photolysis. Evidence is presented for the occurrence of photoionization from the charge-transfer-to-solvent (CTTS) excited state of N3(-). The azide radical which results from this process was identified spectroscopically and some of its properties were investigated. Only about 15% of the CTTS excited ions undergo photoionization and the rest produce NH2OH, possibly by first being internally converted to the n, pi* state. Ammonia is produced from the reduction of hydroxylamine by solvated electrons. This is indicated by the effect of electron scavengers on the photolysis of N3(-) at 2144A. The study of the photochemistry of NCS(-) has been completed and its relation to the photochemistry of N3(-) is discussed. (Author)