物理化学学报 >> 2010, Vol. 26 >> Issue (09): 2535-2542.doi: 10.3866/PKU.WHXB20100931

量子化学及计算化学 上一篇    下一篇

N—O键解离焓的密度泛函理论研究

郑文锐, 徐菁利, 熊瑞   

  1. 上海工程技术大学化学化工学院, 上海 201620
  • 收稿日期:2010-05-04 修回日期:2010-06-01 发布日期:2010-09-02
  • 通讯作者: 郑文锐, 徐菁利 E-mail:wrzheng@sues.edu.cn, xujingli@sues.edu.cn
  • 基金资助:

    上海优青科研基金(B-8500-08-0110),校启基金(08-22)和创新项目基金(cx0904009)资助项目

Density Functional Theory Study on N—O Bond Dissociation Enthalpies

ZHENG Wen-Rui, XU Jing-Li, XIONG Rui   

  1. College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai 201620, P. R. China
  • Received:2010-05-04 Revised:2010-06-01 Published:2010-09-02
  • Contact: ZHENG Wen-Rui, XU Jing-Li E-mail:wrzheng@sues.edu.cn, xujingli@sues.edu.cn
  • Supported by:

    The project was supported by the Foundation of Shanghai Excellent Youth (B-8500-08-0110), School Start-Up Fund (08-22) and Innovation Fund (cx0904009), China.

摘要:

在高精度计算方法G3 和G3B3 的基础上, 比较了密度泛函理论(DFT)十几种方法对N—O 键解离焓 (BDE) 相对于实验值的计算精度,发现用B3P86 方法计算15 种化合物N—O键的BDE, 均方根误差最小, 仅为 6.36 kJ·mol-1,计算值与实验值的线性相关系数为0.991.在此基础上, 用该方法分别计算了非芳香化合物及芳香化合物的N—O键BDE. 通过自然键轨道分析, 发现部分N—O 键的BDE 与N—O 键的键长、原子电荷密度及键级之间存在定量关系.此外,在B3P86方法的基础上预测了几种典型的杂环芳香化合物N—O键BDE值.

关键词: 密度泛函理论, 键解离焓, 自然键轨道分析, N—O 键

Abstract:

A number of density functional theory (DFT) methods were compared for the calculation of N—O bond dissociation enthalpies (BDEs) with the experimental values on the basis of the high-precision calculation methods G3 and G3B3. We found that the B3P86 method gave the lowest root of mean square error of 6.36 kJ·mol-1 for calculating N—O BDE of 15 molecules and the correlation coefficient between the theoretical and experimental values was 0.991. We, therefore, used this method to calculate the N—O BDEs of non-aromatic and aromatic compounds. Using natural bond orbital analysis, quantitative relationships between some N—O BDEs and the corresponding N—O bond lengths, atomic charges, bond orders were determined. In addition, we predicted the N—O BDEs of several typical heterocyclic aromatic compounds using the B3P86 method.

Key words: Density functional theory, Bond dissociation enthalpy, Natural bond orbital analysis, N—O bond

MSC2000: 

  • O641