Abstract
The translational energy spectrum of H Rydberg atoms resulting from the photolysis of methanethiol (CH 3SH) at 216 nm includes peaks which arise from the secondary photolysis of methyl radicals—one of the primary products. The measured times of flight of these secondary H atoms indicate that the partner CH 2 fragments resulting from predissociation of CH 3(B̃) radicals are formed predominantly in their ground (X̃ 3B 1) electronic state rather than the ã 1A 1 excited state as previously presumed. The dynamics of this dissociation are discussed and rationalised in the light of two coupled model potential energy surfaces for CH 3→CH 2+H.
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