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首页> 外文期刊>The Journal of Chemical Physics >Gas-phase ion chemistry and ab initio theoretical study of phosphine. II. Reactions of PH+ with PH3
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Gas-phase ion chemistry and ab initio theoretical study of phosphine. II. Reactions of PH+ with PH3

机译：膦的气相离子化学和从头算的理论研究。二。 PH +与PH3的反应

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The gas-phase ion chemistry of phosphine has been investigated by ab initio theoretical calculations and experimental techniques. Following a previous study of H and H-2 loss pathways from the P-3-PH3+ adduct (generated by P-3(+) reacting with PH3), the quantum chemical study of these processes has been extended to the ion-molecule reactions starting from (PH+)-P-2 reacting with PH3, as observed by ion trapping. In these experiments, PH+ reacts to give P2Hn+ (n = 2,3) product ions, with loss of H-2 or H in different pathways, and also reacts in charge-exchange processes to form PH and PH3+. Moreover, elimination of two hydrogen molecules has been observed leading to the formation of the P-2(+) ion species. All these processes take place at similar rates, their constants ranging from 1.2 to 5.5 x 10(-10) cm(3) molecule(-1) s(-1). The geometrical structures and energies of transition structures, reaction intermediates, and final products have been determined by ab initio theoretical methods. The initial step is formation of the (HP)-H-2-PH3+ adduct. Then, a hydrogen atom can be directly lost either from dicoordinated or tetracoordinated phosphorus, to give P-3-PH3+ or (HP)-H-1=PH2+, respectively. Alternatively, one hydrogen can first undergo a displacement from the latter to the former P atom to give (H2P)-H-2-PH2+. This migration can then be followed by P-H bond dissociation, yielding again (HP)-H-1=PH2+. Dissociation of H-2 can also occur, from either the initial HPPH3+ or rearranged H2P-PH2+ isomeric ions, yielding the (HP)-H-2=PH+ or (H2P)-H-2=P+ tons, respectively. These last species are related by a H-migration process. A last H-2 loss from H2P = P+ produces P-2(2)+. Other pathways were explored, but proved not to be viable. The heats of formation of the P2Hn+ (n = 0-4) ionic species have also been computed and reported with the experimental data in the literature. (C) 1998 American Institute of Physics. [S0021-9606(98)30548-6]. [References: 70]
机译：通过从头开始的理论计算和实验技术研究了膦的气相离子化学。在先前研究了P-3-PH3 +加合物（由P-3（+）与PH3反应生成）的H和H-2丢失途径之后，这些过程的量子化学研究已扩展到离子分子反应从（PH +）-P-2与PH3反应开始，这是通过离子捕获法观察到的。在这些实验中，PH +反应生成P2Hn +（n = 2,3）产物离子，并在不同途径中损失H-2或H，并且在电荷交换过程中反应形成PH和PH3 +。此外，已观察到消除两个氢分子导致形成P-2（+）离子物种。所有这些过程均以相似的速率发生，其常数范围为1.2至5.5 x 10（-10）cm（3）分子（-1）s（-1）。过渡结构，反应中间体和最终产物的几何结构和能量已通过从头算的理论方法确定。第一步是形成（HP）-H-2-PH3 +加合物。然后，氢原子可以直接从二配位或四配位的磷中丢失，分别得到P-3-PH3 +或（HP）-H-1 = PH2 +。或者，一个氢可以首先从后者到前一个P原子发生置换，得到（H2P）-H-2-PH2 +。然后，该迁移之后可以进行P-H键解离，再次产生（HP）-H-1 = PH2 +。从初始的HPPH3 +或重排的H2P-PH2 +异构离子也可能发生H-2的解离，分别产生（HP）-H-2 = PH +或（H2P）-H-2 = P +吨。这些最后的物种与H迁移过程相关。来自H2P = P +的最后H-2损失产生P-2（2）+。探索了其他途径，但被证明是不可行的。还已经计算出P2Hn +（n = 0-4）离子物质的形成热，并用文献中的实验数据进行了报道。 （C）1998美国物理研究所。 [S0021-9606（98）30548-6]。 [参考：70]

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