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极低温度下旋转激发的同核双原子分子与离子碰撞中络合物形成的速率:应用于氢同位素和含氢离子。

Rates of complex formation in collisions of rotationally excited homonuclear diatoms with ions at very low temperatures: application to hydrogen isotopes and hydrogen-containing ions.

作者信息

Dashevskaya E I, Litvin I, Nikitin E E, Troe J

机构信息

Department of Chemistry, Technion--Israel Institute of Technology, Haifa 32000, Israel.

出版信息

J Chem Phys. 2005 May 8;122(18):184311. doi: 10.1063/1.1889425.

Abstract

State-selected rate coefficients for the capture of ground and rotationally excited homonuclear molecules by ions are calculated, for low temperatures, within the adiabatic channel classical (ACCl) approximation, and, for zero temperature, via an approximate calculation of the Bethe limit. In the intermediate temperature range, the accurate quantal rate coefficients are calculated for j = 0 and j = 1 states of hydrogen isotopes (H2, HD, and D2) colliding with hydrogen-containing ions, and simple analytical expressions are suggested to approximate the rate coefficients. For the ground rotational state of diatoms, the accurate quantal rate coefficients are higher compared to their ACCl counterparts, while for the first excited rotational state the reverse is true. The physical significance of quantum effects for low-temperature capture and the applicability of the statistical description of capture are considered. Particular emphasis is given to the role of Coriolis interaction. The relevance of the present capture calculations for rates of ortho-para conversion of H2 in collisions with hydrogen-containing ions at low temperatures is discussed.

摘要

计算了离子捕获基态和转动激发的同核分子的态选择速率系数,对于低温情况,在绝热通道经典(ACCl)近似下进行计算,对于零温度情况,通过对贝塞极限的近似计算得出。在中间温度范围内,计算了氢同位素(H₂、HD和D₂)的j = 0和j = 1态与含氢离子碰撞时的精确量子速率系数,并给出了简单的解析表达式来近似速率系数。对于双原子分子的基态转动,精确的量子速率系数比其ACCl对应值更高,而对于第一激发转动态则相反。考虑了低温捕获中量子效应的物理意义以及捕获统计描述的适用性。特别强调了科里奥利相互作用的作用。讨论了当前捕获计算对于低温下H₂与含氢离子碰撞时正 - 仲转换速率的相关性。

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