Group effect on ionization potential for mono‐substituted aliphatic compounds. (20th May 2015)

• Record Type: Journal Article
• Authors: Chen, Guanfan; Tang, Mengzhuo; Zeng, Rongjin; Liu, Wanqiang; Cao, Chenzhong
• Is Part Of: Journal of physical organic chemistry. Volume 28:Number 9(2015:Sep.)
• Page Start: 612
• Page End: 616
• Publication Date: 2015-05-20
• Subjects: Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.3459
• Languages: English
• ISSNs: 0894-3230

Abstract

<abstract abstract-type="main"> <title>Abstract</title> <p>The group effect on ionization potential for <italic>mono</italic>‐substituted aliphatic compounds RX was investigated, and it was found that there is a good relationship between the ionization potential (<italic>IP</italic>) and the parameters, group electronegativity <italic>χ</italic>_{eq, X}, the group polarizability ∑<italic>PEI</italic>_X, and the disperse contribution of single non‐bond electron <italic>E_dc</italic> for titled compounds, and these parameters earlier were easily calculated from the molecular structure. Moreover, the B3LYP density functional method was also employed to estimate <italic>IP</italic> values of the same <italic>mono</italic>‐substituted aliphatic compounds. The results showed that it was difficult to get reliable ionization data using DFT method, and the regression equation with descriptors <italic>χ</italic>_{eq, X}, ∑<italic>PEI</italic>_X, and <italic>E_dc</italic> was more effective than DFT method in predicting <italic>IP</italic> values for titled compounds. The results are helpful to understand the role of group effect on molecular properties. Copyright © 2015 John Wiley &amp; Sons, Ltd.</p> </abstract>