取代苯甲酸羧基上H和O原子的部分电荷与Hammett常数之间的线性关系

高等学校化学学报 ›› 2009, Vol. 30 ›› Issue (11): 2233.

取代苯甲酸羧基上H和O原子的部分电荷与Hammett常数之间的线性关系

李化毅, 胡友良

中国科学院化学研究所, 高分子科学与材料联合实验室, 工程塑料重点实验室, 北京 100190

收稿日期:2009-01-05 出版日期:2009-11-10 发布日期:2009-11-10
通讯作者: 李化毅, 男, 博士, 副研究员, 主要从事烯烃配位聚合及聚烯烃新材料的研究. E-mail: liweike@iccas.ac.cn
基金资助:
国家自然科学基金(批准号: 20334030, 50703044 和 20734002)资助.

Linear Relationship Between the Partial Charges of H and O Atoms in Carboxyl of Substituted Benzoic Acid and the Hammett Constants

LI Hua-Yi*, HU You-Liang

Joint Laboratory of Polymer Science and Materials, Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Received:2009-01-05 Online:2009-11-10 Published:2009-11-10
Contact: LI Hua-Yi. E-mail: liweike@iccas.ac.cn
Supported by:
国家自然科学基金(批准号: 20334030, 50703044 和 20734002)资助.

摘要/Abstract

摘要：

采用密度泛函分析了取代苯甲酸中羧基上的H1原子和2个氧原子O2和O3的电荷与取代基的Hammett常数之间的线性关系. 比较了不同密度泛函和电荷计算方法B3LYP/6-311G*/(NBO, Mulliken), (BLYP, BP, PWC)/DNP/(Hirshfeld, Mulliken)对上述线性相关系数的影响. 结果表明, BLYP/DNP/Hirshfeld方法的计算精度高且计算速度快. 使用BLYP/DNP/Hirshfeld方法计算了70个取代苯甲酸的部分电荷, 发现H1, O2和O3原子的电荷与取代基Hammett常数σ_p和σ_m之间的线性相关系数可达到0.98以上, 其中O2的电荷和Hammett常数的线性相关性最好. O2的电荷值可以作为Hammett常数的替代, 用于结构性能定量分析, 也可以用于预测取代基的Hammett常数.

关键词: Hammett常数; 密度泛函理论; 原子电荷; 苯甲酸

Abstract:

The linear dependence between the partial charges of H1, O2 and O3 atoms in carboxyl of substituted benzoic acid and Hammett constants was analyzed by density functional theory(DFT). Different density functional and partial charge computation methods[B3LYP/6-311G*/(NBO, Mulliken), (BLYP, BP, PWC)/DNP/(Hirshfeld, Mulliken)] were used to evaluate the above linear relationship. It was found that BLYP/DNP/Hirshfeld had high accuracy and high computational speed. Seventy substituted benzoic acid compounds were computed. The results show that the linear correlation coefficient between the partial charges of H1, O2 and O3 atoms and σ_p and σ_m is higher than 0.98. The best linear relationship occurred between the partial charge of O2 atom and Hammett constant. The partial charge of O2 atom could be used as substitute of Hammett constant in the quantitative structure property analysis and to predict Hammett constant.

Key words: Hammett constant; Density functional theory; Atom charge; Benzoic acid

TrendMD:

李化毅, 胡友良. 取代苯甲酸羧基上H和O原子的部分电荷与Hammett常数之间的线性关系. 高等学校化学学报, 2009, 30(11): 2233.

LI Hua-Yi*, HU You-Liang. Linear Relationship Between the Partial Charges of H and O Atoms in Carboxyl of Substituted Benzoic Acid and the Hammett Constants. Chem. J. Chinese Universities, 2009, 30(11): 2233.