Department of Chemistry, Wayne State University, Detroit, Michigan 48202, USA.
J Phys Chem A. 2011 Jun 30;115(25):7105-11. doi: 10.1021/jp112427r. Epub 2011 Apr 14.
Product branching ratios (BRs) are reported for ion-molecule reactions of state-prepared nitrogen cation (N(2)(+)) with methane (CH(4)), acetylene (C(2)H(2)). and ethylene (C(2)H(4)) at low temperature using a modified ion imaging apparatus. These reactions are performed in a supersonic nozzle expansion characterized by a rotational temperature of 40 ± 5K. For the N(2)(+) + CH(4) reaction, a BR of 0.83:0.17 is obtained for the dissociative charge-transfer (CT) reaction that gives rise to the formation of CH(3)(+) and CH(2)(+) product ions, respectively. The N(2)(+) + C(2)H(2) ion-molecule reaction proceeds through a nondissociative CT process that results in the sole formation of C(2)H(2)(+) product ions. The reaction of N(2)(+) with C(2)H(4) leads to the formation of C(2)H(3)(+) and C(2)H(2)(+) product ions with a BR of 0.74:0.26, respectively. The reported BR for the N(2)(+) + C(2)H(4) reaction is supportive of a nonresonant dissociative CT mechanism similar to the one that accompanies the N(2)(+) + CH(4) reaction. No dependence of the branching ratios on N(2)(+) rotational level was observed. In addition to providing direct insight into the dynamics of the state-prepared N(2)(+) ion-molecule reactions with the target neutral hydrocarbon molecules, the reported low-temperature BRs are also important for accurate modeling of the nitrogen-dominated upper atmosphere of Saturn's moon, Titan.
产物分支比(BR)是通过低温下使用改进的离子成像仪对态制备氮阳离子(N(2)(+))与甲烷(CH(4))、乙炔(C(2)H(2))和乙烯(C(2)H(4))的离子-分子反应进行报告的。这些反应是在超音速喷嘴膨胀中进行的,旋转温度为 40 ± 5K。对于 N(2)(+) + CH(4)反应,得到分别为 CH(3)(+)和 CH(2)(+)产物离子的离解电荷转移(CT)反应的 BR 为 0.83:0.17。N(2)(+) + C(2)H(2)离子-分子反应通过非离解 CT 过程进行,导致仅形成 C(2)H(2)(+)产物离子。N(2)(+)与 C(2)H(4)的反应导致 C(2)H(3)(+)和 C(2)H(2)(+)产物离子的形成,BR 分别为 0.74:0.26。报告的 N(2)(+) + C(2)H(4)反应的 BR 支持类似于伴随 N(2)(+) + CH(4)反应的非共振离解 CT 机制。没有观察到 BR 对 N(2)(+)旋转能级的依赖性。除了直接了解态制备 N(2)(+)离子-分子与靶中性烃分子的反应动力学外,报告的低温 BR 对于准确模拟土星卫星土卫六的氮主导高层大气也非常重要。