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基于燃烧详细反应机理构建的需要,采用反应类过渡态理论(RC-TST)研究了OH自由基夺取烷基环戊烷环上和侧链上氢原子的动力学.在考察侧链氢提取反应类的16个代表反应的基础上,本工作首次将该方法推广到环上α氢提取反应类的10个代表反应的研究,分别建立了两类反应的线性自由能(LER)关系式.计算结果表明,采用RC-TST/LER方法预测的这两类反应的速率常数与直接应用TST/Eckart方法得到的结果接近,说明RC-TST/LER方法对预测这两类反应的速率常数非常有效,且节约了大量计算成本.而且,无论是侧链还是五元环,OH夺取叔碳上的氢原子最易发生.
Based on the detailed reaction mechanism of combustion, the kinetics of OH radical scavenging hydrogen atoms on the alkylcyclopentane ring and side chain was studied by the reaction-state transition state theory (RC-TST) Based on the 16 representative reactions of this class, this work for the first time extended the method to the 10 representative reactions of the α-hydrogen extraction reaction on the ring and established the linear free energy (LER) relationship for the two types of reactions, respectively. The results show that the rate constant of these two types of reactions predicted by RC-TST / LER method is close to that obtained by the direct application of TST / Eckart method, indicating that the RC-TST / LER method is very effective in predicting the rate constants of these two types of reactions, And save a lot of computing costs.And, whether it is a five-membered ring or side chain, OH captures the most likely to occur on the tertiary carbon hydrogen atoms.