共轭烃中的非键分子轨道

介绍了采用“标注星号”求解共轭交替烃非键分子轨道(NBMO)的方法. 对于奇数碳交替烃，其NBMO的线性组合系数满足“零和规则”，因此只需要设定一个待定系数，然后对各原子轨道的组成系数进行归一化处理，便可求得NBMO的表达式，并确定各个碳原子处的电荷密度. 而一些偶数碳交替烃也可能存在NBMO，在计算过程中可以将偶数碳交替烃拆分成数个奇数碳交替烃，通过设置多个参数进行求解. 本文结合“星号标注法”求解奇、偶交替共轭烯烃分子中非键分子轨道的实例，结合DFT计算，对共轭交替烃中的非键分子轨道进行了讨论与分析.

The Non-Bonding Molecular Orbitals in Conjugated Hydrocarbons

The NBMO of alternant hydrocarbons could be determined by the “star notation” method. The coefficients of the NBMO of odd alternant hydrocarbons are easy to be calculated using the “zero-sum rule” through undetermined coefficient method. Since multiple NBMOs may exist in some even alternant hydrocarbons, more than one algebra number must be employed for the star notation in the determination of the coefficients. A good agreement was observed between the results from “star notation” method and DFT calculations.