Demonstration of the branching ratio inversion for the electron attachment to phosphoryl chloride POCl3 in the gas phase between 300 and 200 K

Electron attachment to phosphoryl chloride (phosphorus oxychloride) POCl3 has been studied in the gas phase by mass spectrometry at several low temperatures (47.7, 74.5, 169.7 and 199.5K) with the CRESU method. By measuring over this temperature range and data from [8], we have demonstrated the inversion of the branching ratio between the exothermic non-dissociative exit channel POCl3− and the thermo-neutral dissociative exit channel POCl2− + Cl. A kinetic model in terms of statistical theory is used to fit the experimental data.