Unimolecular Dissociation Dynamics of Vinylchloride on the Ground Electronic Potential Energy Surface: Excitation by Chemical Activation and the Product State Distributions of HCl and Cl Fragments

초록

Photodissociation dynamics of 3-methyl-3-chlorodiazirine was investigated by measuring the rovibrational and translational energy contents of the N2 fragments formed in the CN2 ring breaking. The internal and translational energy distributions of N2 fragments were measured with (2+1) resonantly enhanced multiphoton ionization (REMPI) combined with mass-selective time-of-flight mass spectrometry. The N2 fragments are found to be rotationally hot (J~60) suggesting stepwise breaking of two C-N bonds. The large translational energy is also consistent with the stepwise bond breaking model that the exit channel barrier for the second C-N bond breaking is so steep that the carbene and N2 fragments exert a strong repulsion force each other during separation.