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首页> 外文期刊>Chemical Physics: A Journal Devoted to Experimental and Theoretical Research Involving Problems of Both a Chemical and Physical Nature >Reaction mechanism, rate constants, and product yields for the oxidation of embedded five-member ring radicals with atomic oxygen
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Reaction mechanism, rate constants, and product yields for the oxidation of embedded five-member ring radicals with atomic oxygen

机译:反应机理,速率常数和产物产生嵌入的五个成员环自由基的氧化原子氧气

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摘要

Oxidation mechanism of an embedded five-member ring on a surface of a carbonaceous particle with atomic oxygen has been studied employing G3(MP2,CC)//B3LYP/6-311G* potential energy surface calculations for C15H9 + O reactions. Temperature- and pressure-dependent reaction rate constants have been evaluated using the RRKM - Master Equation approach. The mechanism involves barrierless oxygen atom addition to a carbon atom on a free edge of a five-member ring followed by migration of the H atom from the attacked C atom to an ortho position followed by the five-member ring opening and elimination of the CO group, with the five-member ring being fully destroyed. When the embedded ring has three common sides with surrounding six-member rings and one free-edge carbon atom, the only product is the 4-phenanthrenyl radical. When the embedded ring has two common sides with the six-member rings and two free-edge C atoms, two different decarbonylation products possessing a phenalene core can be formed depending on the direction of the 1,2-H shift.
机译:研究了用G3(MP2,CC)// B3LYP / 6-311G * C15H9 + O反应的含有原子氧的碳质颗粒表面上的嵌入式五构件环的氧化机理。使用RRKM - 总体方程方法评估了温度和压力依赖性反应速率常数。该机制涉及在五个成员环的自由边缘上的碳原子的禁止氧原子,然后通过将H原子从攻击的C原子迁移到邻位位置,然后是五个成员环开口和消除CO小组,五个成员戒指完全被摧毁。当嵌入环有三个共同侧面具有周围的六个构件环和一个自由边缘碳原子时,唯一的产物是4-菲自由基。当嵌入环具有两个共同的侧面时具有六个构件环和两个自由边缘C原子,可以根据1,2-H偏移的方向形成具有具有吩氢芯的两种不同的脱羰产物。

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