Citation: ZHONG Aiguo, LI Rongrong, HONG Qin, ZHANG Jie, CHEN Dan. Understanding the Isomerization of Monosubstituted Alkanes from Energetic and Information-Theoretic Perspectives[J]. Acta Physico-Chimica Sinica, ;2018, 34(3): 303-313. doi: 10.3866/PKU.WHXB201708302 shu

Understanding the Isomerization of Monosubstituted Alkanes from Energetic and Information-Theoretic Perspectives

College of Medicine and Chemical Engineering, Taizhou University, Taizhou 318000, Zhejiang Province, P. R. China

Corresponding author: ZHONG Aiguo, zhongaiguo@tzc.edu.cn
Received Date: 19 July 2017
Revised Date: 16 August 2017
Accepted Date: 24 August 2017
Available Online: 30 March 2017
Fund Project: the Natural Science Foundation of Zhejiang Province, China LY15B030001The project was supported by the Natural Science Foundation of Zhejiang Province, China (LY15B030001, LY15B060001) and Zhejiang Province Undergraduate Student Innovation Project, China (2017R430014)the Natural Science Foundation of Zhejiang Province, China LY15B060001Zhejiang Province Undergraduate Student Innovation Project, China 2017R430014

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 C_nH_2n+1―R (n = 3, 4, 5, 6; R = OH, OCH₃, NH₂, NO₂, F, Cl, 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 E_e and the Fisher information or Shannon entropy.
- Molecular stability,
- Steric hindrance,
- Density functional theory,
- Energy component
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