Intermediates in the γ-radiolysis of diraient sulfur compounds in dilute glass matrices

Abstract

The optical spectra of the charged ions obtained from γ-irradiation of dilute alkyl mercaptans, sulfides, and disulfides in a variety of dilute rigid glasses are measured at 77 K. The photochemical stability of these ions is determined. A new photochromic species has been found. It is derived from a mercaptan dimer cation and is analogous to the photochromic anion produced from alkyl disulfides. The results of γ-radiation are compared to the uv photolysis of similar matrices, and it is found that the thiyl (RS•) and perthiyl radicals (RS2•) are not generally in evidence in γ-irradiated matrices although they may be obtained by appropriate annealing or photobleaching of the irradiated matrix. The ions which have been characterized optically are RSH+, RSH−, RSSR+ or their dimers, and RSS(H)R. The relative stabilities of these species in the low temperature glasses are determined.