论文标题

在星际温度下建模离子反应:NH2- + H2 <-> NH3 + H-的情况

Modeling ionic reactions at interstellar temperatures: the case of NH2- + H2 <--> NH3 + H-

论文作者

Gianturco, F. A., Yurtsever, E., Satta, M., Wester, R.

论文摘要

我们在本文中介绍了标题反应的能量曲线的主要结构特征和焓细节,均针对NH $ _ {3} $形成的放热(前向)路径,以及对NH $ _ {2}^{ - }^{ - } $ for的热热(反向)反应。两种系统都与星际介质(ISM)中的氮化学相关。它们也有助于记录H $^{ - } $在温度低于室温下的分子云中的可能作用。结构计算是使用从头算法进行的,并进一步采用以获取对早期实验中检测到的星际温度的反应速率。反应速率是使用变异过渡状态理论(VTST)方法从计算的最低能量路径(MEP)获得的。结果表明,一旦我们详细分析了反应物理学并相应地修改VTST方法,就可以很好地描述与室温下的实验相符,而在室温下的实验非常好。这是通过使用T依赖性缩放的,从室温条件到下部ISM温度,这可以承认快速,无障碍的放热反应的非规范行为。在我们的主要文本中讨论的早期工作中也提出了此功能。详细讨论了实验行为的物理原因,以及从室温远离室温时需要改善VTST方法的需求。

We present in this paper the main structural features and enthalpy details for the energy profiles of the title reactions, both for the exothermic (forward) path to NH$_{3}$ formation and for the endothermic (reverse) reaction to NH$_{2}^{-}$ formation. Both systems have relevance for the nitrogen chemistry in the interstellar medium (ISM). They are also helpful to document the possible role of H$^{-}$ in molecular clouds at temperatures well below room temperature. The structural calculations are carried out using ab initio methods and are further employed to obtain the reaction rates down to the interstellar temperatures detected in earlier experiments. The reaction rates are obtained from the computed Minimum Energy Path (MEP) using the Variational Transition State Theory (VTST) approach. The results indicate very good accord with the experiments at room temperature, while the measured low temperature data down to 8 K are well described once we analyse in detail the physics of the reactions and modify accordingly the VTST approach. This is done by employing a T-dependent scaling, from room temperature conditions down to the lower ISM temperatures, which acknowledges the non-canonical behavior of the fast, barrierless exothermic reaction. This feature was also suggested in the earlier work discussed below in our main text. The physical reasons for the experimental behavior, and the need for improving on the VTST method when used away from room temperatures, are discussed in detail.

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