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Gas-Phase Reaction Kinetics of Pyruvic Acid with OH Radicals: The Role of Tunneling, Complex Formation, and Conformational Structure.
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-01-23 , DOI: 10.1021/acs.jpca.9b09638 Jonathan R Church 1 , Veronica Vaida 1 , Rex T Skodje 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-01-23 , DOI: 10.1021/acs.jpca.9b09638 Jonathan R Church 1 , Veronica Vaida 1 , Rex T Skodje 1
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The gas-phase reaction of pyruvic acid (PA) with the OH radical is studied theoretically using accurate quantum chemistry and transition state theory. Two chemically distinct H-atom abstraction reactions and two distinct OH addition reactions have been identified. The rate coefficients for these four processes were calculated. Quantum tunneling was included in each rate using the small curvature tunneling method. The influence of the conformational structure of PA was found to be particularly intriguing. While the trans-cis structure was found to dominantly react by H-atom abstraction from the methyl site, the trans-trans conformer was found to react mostly through H-atom abstraction from the acid site. A general formalism was developed to model the kinetics of the reactions that involve multiple conformers, interconverting prereactive complexes, and multiple transition states. Comparison of the results obtained with available experimental rate observations reveals agreement with the trans-trans conformer of PA but disagreement with the results obtained for a full statistical mixture of reagents. The role of these reactions in the atmospheric processing of PA is discussed.
中文翻译：
丙酮酸与OH自由基的气相反应动力学：隧穿，络合物形成和构象结构的作用。
使用精确的量子化学和过渡态理论从理论上研究了丙酮酸（PA）与OH自由基的气相反应。已经鉴定出两个化学上不同的H原子抽象反应和两个不同的OH加成反应。计算了这四个过程的速率系数。使用小曲率隧穿方法将量子隧穿包括在每个速率中。发现PA的构象结构的影响特别令人着迷。虽然发现反式顺式结构主要通过从甲基位点的H原子抽象反应来进行反应，但发现反式反式构象异构体主要通过从酸性位点的H原子抽象反应进行反应。人们开发了一种通用形式主义，以对涉及多个构象异构体，相互转化预反应性络合物，以及多个过渡状态。将所得结果与可用的实验速率观察结果进行比较，发现与PA的反式-反式构象异构体一致，但与试剂的完全统计混合物所得的结果不一致。讨论了这些反应在PA的大气处理中的作用。
更新日期：2020-01-23
中文翻译：
丙酮酸与OH自由基的气相反应动力学：隧穿，络合物形成和构象结构的作用。
使用精确的量子化学和过渡态理论从理论上研究了丙酮酸（PA）与OH自由基的气相反应。已经鉴定出两个化学上不同的H原子抽象反应和两个不同的OH加成反应。计算了这四个过程的速率系数。使用小曲率隧穿方法将量子隧穿包括在每个速率中。发现PA的构象结构的影响特别令人着迷。虽然发现反式顺式结构主要通过从甲基位点的H原子抽象反应来进行反应，但发现反式反式构象异构体主要通过从酸性位点的H原子抽象反应进行反应。人们开发了一种通用形式主义，以对涉及多个构象异构体，相互转化预反应性络合物，以及多个过渡状态。将所得结果与可用的实验速率观察结果进行比较，发现与PA的反式-反式构象异构体一致，但与试剂的完全统计混合物所得的结果不一致。讨论了这些反应在PA的大气处理中的作用。
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