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• 作者：John C. Poutsma ; Anthony J. Midey ; Timothy H. Thompson ; Albert A. Viggiano
• 刊名：Journal of Physical Chemistry A
• 出版年：2006
• 出版时间：October 5, 2006
• 年：2006
• 卷：110
• 期：39
• 页码：11315 - 11319
• 全文大小：103K
• 年卷期：v.110,no.39(October 5, 2006)
• ISSN：1520-5215

文摘

The absolute rate coefficients and product ion branching percentages at 298 K for the reactions of severalPO_xCl_y^- species with atomic nitrogen (N (⁴S_3/2)) and atomic oxygen (O (³P)) have been determined in aselected-ion flow tube (SIFT) instrument. PO_xCl_y^- ions are generated by electron impact on POCl₃ in a high-pressure source. O atoms are generated by quantitative titration of N atoms with NO, where N atoms areproduced by microwave discharge on N₂. The experimental procedure allows for the determination of ratecoefficients for the reaction of the reactant ion with N (⁴S_3/2) and O (³P) as well as with N₂ and NO. Noneof the ions react with N₂ or NO, giving an upper limit to the rate coefficient of <5 × 10^-12 cm³ molecules^-1s^-1. POCl₃^- and POCl₂^- do not react with N atoms, giving an upper limit to the rate coefficient of <1 ×10^-11 cm³ molecules^-1 s^-1. The major product ion for POCl₃^- and POCl₂^- reacting with O involves loss ofCl from the reactant ion, accounting for >85% of the products. PO₂^- is a minor product (4%) from POCl₂^-+ O. Only PO₂Cl^- reacts with both N and O, directly giving PO₂^- and PO₃^- as major products. In addition,calculations of the structures and energies for PO₂N, PO₂N^-, and NCl have been performed at the G3 levelof theory to obtain estimates for the energetics of the PO₂Cl^- reactions. PO₂^-, PO₃^-, and PO₂Cl₂^- are allunreactive with both N and O. Comparisons of the reactivity of PO_xCl_y^- ions with O atoms are made toprevious reactivity studies of these ions. In particular, routes that yield the very stable PO₂^- and PO₃^- ionsare discussed.