Transient spectra and primary processes in the flash photolysis of CH3SSCH3, CH3SCH3, CH3SH and C2H5SH

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Abstract
From direct observation of the CH3, CH3S, CH2S and S2 produced in the flash photolysis of CH3SSCH3(1950 Å) it was concluded that the primary processes are : [graphic ommitted] The relative degree of S—S to C—S bond scission was recorded as 1.35. The stability of CH3S and the instability of CH3SS are consistent with statistical partitioning of the excess energy. From the independence of the CH3S and CH3 on total pressure in the 1950 Å flash photolysis of CH3SCH3, it was concluded that the primary process is predominantly CH3SCH3+hν→CH3+CH3S. The stability of the generated CH3S is consistent with the statistical energy partitioning. By assuming equal yields of CH3 and CH3S radicals, the oscillator strength of the CH3S band at 2185 Å was 1.3(±0.2)× 10–3. Two primary processes were identified in the 1950 Å flash photolysis of CH3SH, [graphic ommitted] and the relative degree of C—S to S—H bond cleavage was 1:1.7. It was suggested that in this case the excited CH3SH finds a configuration in which the S—H potential is repulsive more rapidly than the rate at which the energy is partitioned. To account for the pressure dependent formation of CH3 and CH2S in the 1950 Å flash photolysis of C2H5SH, and also the independence of CH2S on added nitric oxide, the primary processes [graphic ommitted] were postulated.

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