Effect of pressure and temperature on the competition between nondissociative and dissociative electron attachment to POCl3

Abstract

Branching between the nondissociative, POCl3−, and dissociative, POCl2−, products of the POCl3 electron attachment reaction has been examined as a function of buffer gas pressure and temperature. A strong positive pressure dependence is observed for the nondissociative channel, where at 303 K, the %POCl3− increases from 31% at 1 Torr to 94% at 675 Torr total pressure. Conversely, the dissociative channel displays a strong positive temperature dependence. The effect of pressure and temperature on the relative amounts of POCl3− and POCl2− observed is discussed in terms of the competition between the collisional stabilization and dissociation rates of the POCl3−* excited intermediate. The decomposition of POCl3−* is modeled with Rice–Ramsperger–Kassel decomposition kinetics weighted by the vibrational energy distribution of POCl3 neutrals. This model provides an excellent simulation of the experimental pressure and temperature dependencies of the electron attachment process.