Electron attachment to POCl3. III. Measurement and kinetic modeling of branching fractions

Abstract

Electron attachment to POCl3 was studied in the bath gas He over the pressure range 0.4-3.1 Torr and the temperature range 300-1210 K. Branching fractions of POCl3-, POCl2-, Cl-, and Cl-2(-) were measured. The results are analyzed by kinetic modeling, using electron attachment theory for the characterization of the nonthermal energy distribution of the excited POCl3- anions formed and chemical activation-type unimolecular rate theory for the subsequent competition between collisional stabilization of POCl3- and its dissociation to various dissociation products. Primary and secondary dissociations and/or thermal dissociations of the anions are identified. The measured branching fractions are found to be consistent with the modeling results based on molecular parameters obtained from quantum-chemical calculations. (c) 2011 American Institute of Physics. [doi:10.1063/1.3549139]