Photodissociation dynamics of the methyl perthiyl radical at 248 nm via photofragment translational spectroscopy.

Photofragment translational spectroscopy was used to study the photodissociation of the methyl perthiyl radical CH(3)SS at 248 nm. The radical was produced by flash pyrolysis of dimethyl disulfide (CH(3)SSCH(3)). Two channels were observed: CH(3) + S(2) and CH(2)S + SH. Photofragment translational energy distributions indicate that CH(3) + S(2) results from C-S bond fission on the ground state surface. The CH(2)S + SH channel can proceed through isomerization to CH(2)SSH on the ground state surface but also may involve production of electronically excited CH(2)S.