Collision–Induced Harpooning Observed in the Excimer Formation in the Oriented NF3 + Oriented Kr* (3P2, MJ = 2) Reaction
Collision–Induced Harpooning Observed in the Excimer Formation in the Oriented NF3 + Oriented Kr* (3P2, MJ = 2) Reaction
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在定向 NF3 + 定向 Kr* (3P2, MJ = 2) 反应中准分子形成中观察到的碰撞诱导鱼叉效应
DOI：
10.1021/jp200979r
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发表时间：
2011
期刊：
影响因子：
2.9
通讯作者：
H. Ohoyama
中科院分区：
文献类型：
--
作者：
Y. Matsuura;H. Ohoyama
我们研究了 NF3+ Kr*(3P2) 反应中 KrF* 的形成如何取决于碰撞框架中 NF3 分子的取向和 Kr*(3P2,MJ= 2) 原子排列之间的相互构型。分子空间不透明度函数已确定为碰撞系中原子轨道排列 (ML') 的函数。分子空间不透明度函数很大程度上取决于 ML'； |ML′| = 1取向有利于分子轴方向，而ML' = 0取向有利于横向，在分子轴方向反应性很差。通过从头计算评估了 NF3 几何变形对电子亲和势的影响，并根据溴-稀有气体系统的相互作用势估计了 ML' 相关的分子间势。我们提出“碰撞诱导鱼叉机制”作为一种新的鱼叉过程，其中 NF3 几何形状与 Cs 对称性的碰撞变形作为 NF3− 形成的电子转移的引发因素发挥着重要作用，因为增加了 NF3− 的电子亲和力，并且由于将负电荷定位在 NF3− 阴离子最近的 F 原子上。所有实验观察结果都可以支持碰撞诱导的鱼叉机制。
We have studied how the KrF* formation in the NF3+ Kr*(3P2) reaction depends on the mutual configuration between the orientation of the NF3molecule and the alignment of the Kr*(3P2,MJ= 2) atom in the collision frame. The molecular steric opacity function has been determined as a function of the atomic orbital alignment (ML′) in the collision frame. The molecular steric opacity function turns out to depend remarkably onML′; the |ML′| = 1 alignment is favorable at the molecular axis direction, whereas theML′ = 0 alignment is favorable at the sideways direction with a very poor reactivity at the molecular axis direction. The influence of deformation of the NF3geometry on the electron affinity has been evaluated by ab initio calculation, and theML′ dependent intermolecular potential has been estimated from the interaction potential for the bromine−rare gas system. We propose the “collision-induced harpooning mechanism” as a novel process for the harpooning in which collisional deformation of the NF3geometry withCssymmetry plays an important role as an initiating factor on electron transfer for the formation of NF3−due to increasing the electron affinity of NF3and due to localizing the negative charge on the closest F-atom of NF3−anion. All experimental observations can support the collision-induced harpooning mechanism.