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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Dissociation of toluene cation: A new potential energy surface
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Dissociation of toluene cation: A new potential energy surface

机译：甲苯阳离子的解离：一个新的势能面

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摘要

The potential energy surface (PES) for the formation of tropylium and benzylium ions from toluene cation (1) has been explored theoretically. Quantum chemical calculations at the B3LYP/6-311++G** and G3//B3LYP levels were performed. A pathway to form o-isotoluene (5-methylene-1,3-cyclohexadiene) cation (5) from 1 was found. The isomerization occurs by two consecutive 1,2-H shifts from CH3 to the ortho position of the aromatic ring via a distonic benzenium cation (2), which is also an intermediate in the well-known isomerization of 1 to cycloheptatriene cation (4). Since the barrier for the formation of 2 is the highest in the two isomerization pathways, 1, 4, and 5 are interconvertible energetically prior to dissociation. The benzylium ion can be produced via 5 as well as from 1 and the tropylium ion via 4. Rice-Ramsperger-Kassel-Marcus model calculations were carried out based on the obtained PES. The result agrees with previous experimental observations. From a theoretical analysis of kinetics of the isomerizations and dissociations, we suggest that 5 plays an important role in the formation of C7H7+ from 1.
机译：理论上已经探索了由甲苯阳离子（1）形成对yl和苄基离子的势能面（PES）。进行了B3LYP / 6-311 ++ G **和G3 // B3LYP水平的量子化学计算。发现了从1形成邻异甲苯（5-亚甲基-1,3-环己二烯）阳离子（5）的途径。异构化是通过二甲苯苯阳离子（2）从CH3到芳环的邻位连续两个1,2-H移位而发生的，该苯甲酸也是众所周知的1到环庚三烯阳离子异构化的中间体（4） 。由于形成2的障碍在两个异构化途径中最高，因此1、4和5在分解前在能量上可相互转化。苄基离子可以通过5以及1生成，而对yl离子可以通过4生成。Rice-Ramsperger-Kassel-Marcus模型的模型计算是基于所得的PES进行的。结果与先前的实验观察结果一致。通过对异构化和解离动力学的理论分析，我们认为5在从1形成C7H7 +的过程中起着重要作用。

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