Electron attachment to POCl3. III. Measurement and kinetic modeling of branching fractions |
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Authors: | Shuman Nicholas S Miller Thomas M Viggiano A A Troe Jürgen |
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Institution: | Air Force Research Laboratory, Space Vehicles Directorate, Hanscom Air Force Base, Bedford, Massachusetts 01731-3010, USA. |
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Abstract: | Electron attachment to POCl(3) 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 POCl(3)(-), POCl(2)(-), 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 POCl(3)(-?) anions formed and chemical activation-type unimolecular rate theory for the subsequent competition between collisional stabilization of POCl(3)(-?) 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. |
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