Dynamics of methyl radical formation by 266 nm photolysis of xylenes and mesitylene

The 266 nm photodissociation of three xylene isomers and mesitylene leading to the formation of methyl radical was examined. The kinetic energy release profiles for the methyl radical were almost identical for all the three isomers of xylene and mesitylene, while substantial differences were observed for the corresponding profiles of the co-fragment produced by loss of one methyl group. This observation be attributed to the formation of the methyl radical from alternate channels. The total kinetic energy distribution profiles were rationalized based on the dissociation of {sp2}C–C{sp3} bond in the cationic state, wherein the {sp2}C–C{sp3} bond dissociation energy is lowered relative to the ground state. The dissocaiton in the cationic state follows a resonant three-photon absorption process, resulting in maximum total kinetic energy of about 1.6 – 1.8 eV for the photofragments. A results in. Fitting of the TKER distribution profiles to empirical function reveals that the dynamics of {sp2}C–C{sp3} bond dissociation is insensitive to the position of substitution but marginally dependent on the number of methyl groups.