物理化学学报2018，Vol.34Issue(3)：303-313,11.DOI:10.3866/PKU.WHXB201708302
从能量和信息理论视角理解单取代烷烃的异构化
Understanding the Isomerization of Monosubstituted Alkanes from Energetic and Information-Theoretic Perspectives
摘要
Abstract
A unified explanation for the relative stability of linear and branched alkanes is still lacking,and research in this direction is ongoing.Unlike the conventional orbital-based description,we have employed the density functional theory (DFT) based on the total energy and its components as well as a newly proposed energy partitioning scheme [Liu,S.B.J.Chem.Phys.2007,126,244103].Taking monosubstituted hydrocarbons CnH2n+1-R (n =3,4,5,6;R =OH,OCH3,NH2,NO2,F,CI,CN,CHO) as examples,we have investigated the molecular origin and nature within the framework of the DFT.Our computational results revealed that no such a single energy component that dictates the transformation of the mono-substituted alkane derivatives.By the binary fit of the electrostatic potential and steric hindrance from the new energy decomposition scheme,we unraveled that isomerization is mainly governed by the electrostatic potential,while the steric effect has a minor influence.Moreover,we established a linear relationship between the Shannon entropy difference and the Fisher information difference,which is accordance with previous findings.Further,there was no linear relationship between Ee and the Fisher information or Shannon entropy.关键词
分子稳定性/空间位阻/密度泛函理论/能量分项Key words
Molecular stability/Steric hindrance/Density functional theory/Energy component分类
化学化工引用本文复制引用
钟爱国,李嵘嵘,洪琴,张杰,陈丹..从能量和信息理论视角理解单取代烷烃的异构化[J].物理化学学报,2018,34(3):303-313,11.基金项目
The project was supported by the Natural Science Foundation of Zhejiang Province,China (LY15B030001,LY15B060001) and Zhejiang Province Undergraduate Student Innovation Project,China (2017R430014).浙江省自然科学基金(LY15B030001 （LY15B030001,LY15B060001）
LY15B060001)和浙江省大学生科技创新(2017R430014)资助项目 （2017R430014）
