Air Force Research Laboratory, Space Vehicles Directorate, Hanscom Air Force Base, Bedford, Massachusetts 01731-3010, USA.
J Chem Phys. 2011 Mar 7;134(9):094310. doi: 10.1063/1.3549139.
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.
在浴气 He 中，研究了 POCl(3) 在 0.4-3.1 托和 300-1210 K 温度范围内的电子附加。测量了 POCl(3)(-), POCl(2)(-), Cl(-) 和 Cl(2)(-) 的分支分数。结果通过动力学建模进行了分析，使用电子附加理论来描述形成的激发态 POCl(3)(-∗)阴离子的非热能量分布，并使用化学激活型单分子速率理论来描述随后 POCl(3)(-∗)的碰撞稳定化与其分解为各种分解产物之间的竞争。鉴定了阴离子的初级和次级解离和∕或热解离。测量的分支分数与基于量子化学计算得到的分子参数的建模结果一致。
