摘要
根据量子力学微扰理论,将单官能团取代甲烷(MeZ)和单官能团取代烷烃(RZ)分别当作未微扰体系和受微扰体系,则后者的第一电离能I_(p1(RZ))可由下式估算: I_(p1(RZ))=I_(p1(MeZ))+7.1702Δ_(qz)-1.3949ΔPEI 其中I_(p1(MeZ))为取代甲烷的第一电离能,Δ_(qz)为RZ和MeZ分子中Z上面的部分电荷之差,ΔPEI为基团R和Me的极化效应指数(PEI)之差。对10类单官能团取代烷烃的61个化合物计算结果表明,计算值和实验值之间的平均相对误差仅为0.20％。
If regarding monosubstitued methane (MeZ) and monosubstitued paraffin (RZ) as the unperturbed and perturbed molecules respectively, the first ionization potential, Ip1(RZ) , of the latter can be obtained by the expression:
where the Ip1(MeZ) is the first ionization potential of monosubstitued methane, the Δqz is the difference of partial charge on Z in RZ and MeZ molecules, and the ΔPEI is the difference of polarizability effect index ( PEI) between group R and Me. The results obtained show that the mean relative error is only 0.20% between the calculated and experimental IP1(RZ) values for 61 monosubstitued paraffins.
出处
《有机化学》
SCIE
CAS
CSCD
北大核心
2000年第5期822-826,共5页
Chinese Journal of Organic Chemistry
基金
湖南省教委资助项目
关键词
微扰理论
电离能
极化效应指数
单取代烷烃
perturbation theory, substitued paraffin, ionization potentials, polarizability eflect index(PE1)
