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在密度泛函B3LYP/3-21G(d)水平下研究了D_(3h)-C_(74)与氟原子之间的自由基反应,在笼外一定距离扫描得到了氟原子与C_(74)笼相互作用的势能面,优化代表区中关键点的结构和能量得到了可能的自由基异构体,结果显示D_(34)-C_(74)F有9种自由基异构体。另外,探寻了各自由基异构体之间的过渡态和氟原子在不同关键点之间转化的反应机理,反应路径分析表明在两两异构体之间有且只有一个过渡态,即它们之间的反应是一步反应。除此之外,分析了9种自由基异构体的自旋密度并预测了第二个氟原子进攻的首选位置,同时采用密度泛函理论进一步讨论了由最稳定的自由基异构体加成得到的双氟衍生物C_(74)F_2的稳定性,结果表明第二个自由基氟原子和C_(74)F发生加成反应时主要以1,4-加成为主。
The free radical reaction between D_ (3h) -C_ (74) and fluorine atom was studied at density functional B3LYP / 3-21G (d) level and the fluorine atom and C_ (74) The potential energy surface of cage interaction and the possible free radical is obtained by optimizing the structure and energy of the key points in the representative area. The results show that D_ (34) -C_ (74) F has 9 kinds of free radical isomers. In addition, the reaction mechanism between the transition states of the free-radical isomers and the conversion of fluorine atoms between different key points is explored. The reaction path analysis shows that there is only one transition state between the two isomers, that is, The reaction is a one-step reaction. In addition, the spin density of nine free radical isomers was analyzed and the preferred position of attack for the second fluorine atom was predicted. At the same time, the density functional theory The results showed that the addition of the second free radical fluorine atom to C_ (74) F was dominated by 1,4-addition.