气液界面反应的动力学O (1 d)液态烃。
文章的细节
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引用
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华林C,国王KL、木香烯毫升McKendrick公斤
气液界面反应的动力学O (1 d)液态烃。
J理论物理化学a . 2011年6月30日;115 (25):7210 - 9。doi: 10.1021 / jp200292n。Epub 2011年4月7日。
- PubMed ID
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21473641 (在PubMed]
- 文摘
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气液界面的动态反应的第一电子激发态的原子氧,O ((1) D),表面的液态烃,角鲨烷(C (30) H (62);2、6、10、15、19 23-hexamethyltetracosane)实验研究。转化热O ((1) D)原子被193海里光解产生的低压(名义上1毫托)N (2) O一小段距离(意味着= 6毫米)在不断刷新液体表面角鲨烷。新生的哦(X(2)π,v = 0)反应产物被激光诱导荧光检测(生活)的哦(2)σ(+)- X(2)π(1,0)乐队在同一距离地面。速度分布的反冲哦是通过测量特征的外观配置文件作为photolysis-probe延迟的函数选择的转动能级,N’。转动(部分,精细结构)状态分布也以记录生活激发光谱在选定photolysis-probe延迟。哦v = 0转动分布是附近的双峰和经验可以分解成热(~ 300 K)和温度(~ 6000 K) Boltzmann-temperature组件。有一种强烈的旋转能量激发和翻译之间存在正向关系。然而,冷转动组件仍是一个重要的部分(~ 30%)最快的产品,已大幅superthermal速度。我们估计一个大概的量子产率的3%的上限哦/ O ((1) D)和表面原子碰撞。 By comparison with established mechanisms for the corresponding reactions in the gas phase, we conclude that the rotationally and translationally hot products are formed via a nonstatistical insertion mechanism. The rotationally cold but translationally hot component is most likely produced by direct abstraction. Secondary collisions at the liquid surface of products of either of the previous two mechanisms are most likely responsible for the rotationally and translationally cold products. We do not think it likely, a priori, that they could be produced in the observed significant yield via a statistical insertion mechanism for a molecule the size of squalane embedded in a surrounding liquid surface.
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