Photodissociation dynamics of the tert-butyl radical via photofragment translational spectroscopy at 248 nm

Abstract

The photodissociation dynamics of the tert-butyl radical (t-C₄H₉) were investigated using photofragment translational spectroscopy. The tert-butyl radical was produced from flash pyrolysis of azo-tert-butane and dissociated at 248 nm. Two distinct channels of approximately equal importance were identified: dissociation to H + 2-methylpropene, and CH₃ + dimethylcarbene. Neither the translational energy distributions that describe these two channels nor the product branching ratio are consistent with statistical dissociation on the ground state, and instead favor a mechanism taking place on excited state surfaces.