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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Evidence of Oxidation of Aromatic Hydrocarbons by Chloromethyl Radicals: Reinvestigation of Intersolute Hole Transfer Using Pulse Radiolysis
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Evidence of Oxidation of Aromatic Hydrocarbons by Chloromethyl Radicals: Reinvestigation of Intersolute Hole Transfer Using Pulse Radiolysis

机译：氯甲基自由基氧化芳香烃的证据：使用脉冲辐射分解对溶质空穴转移的再研究

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摘要

Intersolute hole transfer (A~(centre dot +) + B -> A + B~(centre dot +)) was reinvestigated using nanosecond pulse radiolysis in fluid solutions of dichloromethane (A, biphenyl; B, naphthacene, rubrene). Under our new experimental conditions where the concentration of the second solute [B] was kept higher than 0.5 mM, the kinetics of the hole transfer was observed within 500 ns after irradiation, at which time the geminate recombination process with counterpart anionic species was also obaerved. On the basis of the analysis with the Smoluchowski equation, the second-order rate constants of hole transfers were successfully obtained. Moreover, we confirmed the existence of another slow oxidation of the second solute B by the solvent neutral radical CH_2Cl~centre dot formed from the electrons ejected during the initial ionizing process. This reaction is a kind of electron transfer with a charge separation that has never been confirmed, but should generally exist in an irradiated solution of halogenated compounds. In our present case, more than 30% of B~(centre dot +)'s were formed through this side reaction. We clarify the formation of two ion pairs on one ionizing event, which will have a great impact on the understanding of the results of product analyses in radiation chemistry. Examination using ab initio molecular orbital calculation of two dissociative electron transfers is also presented.
机译：在二氯甲烷（A，联苯; B，并四苯，红荧烯）的流体溶液中使用纳秒脉冲辐射分解，重新研究了溶质空穴转移（A〜（中心点+）+ B-> A + B〜（中心点+））。在我们新的实验条件下，第二种溶质[B]的浓度保持在0.5 mM以上，在辐照后500 ns内观察到空穴转移的动力学，这时也发生了与对应的阴离子物质发生的发芽重组过程。在Smoluchowski方程分析的基础上，成功获得了空穴转移的二阶速率常数。此外，我们证实了由溶剂中性自由基CH_2Cl〜中心点引起的第二溶质B的另一次缓慢氧化，该中心点由在初始电离过程中喷射的电子形成。该反应是一种带有电荷分离的电子转移，从未得到证实，但通常应存在于卤代化合物的辐照溶液中。在我们目前的情况下，通过该副反应形成了超过30％的B〜（中心点+）。我们澄清了一次电离事件中两个离子对的形成，这将对辐射化学中产物分析结果的理解产生重大影响。还介绍了使用从头算分子轨道计算两个解离电子转移的方法。

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