物理化学学报 >> 2011, Vol. 27 >> Issue (11): 2553-2558.doi: 10.3866/PKU.WHXB20111017

理论与计算化学 上一篇    下一篇

用GGA密度泛函及其长程、色散校正方法计算各类氢键的结合能

孙涛, 王一波   

  1. 贵州省高性能计算化学重点实验室, 贵阳 550025; 贵州大学化学系, 贵阳 550025
  • 收稿日期:2011-05-06 修回日期:2011-07-07 发布日期:2011-10-27
  • 通讯作者: 王一波 E-mail:ybw@gzu.edu.cn
  • 基金资助:

    国家自然科学基金(20463002)和贵州大学自然科学青年科研基金(2009068)资助项目

Calculation of the Binding Energies of Different Types of Hydrogen Bonds Using GGA Density Functional and Its Long-Range, Empirical Dispersion Correction Methods

SUN Tao, WANG Yi-Bo   

  1. Key Laboratory of Guizhou High Performance Computational Chemistry, Guiyang 550025, P. R. China; Department of Chemistry, Guizhou University, Guiyang 550025, P. R. China
  • Received:2011-05-06 Revised:2011-07-07 Published:2011-10-27
  • Contact: WANG Yi-Bo E-mail:ybw@gzu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20463002) and Natural Science for Youth Foundation of Guizhou University, China (2009068).

摘要: 应用广义梯度近似(GGA) (PW91 和PBE)、含动能密度的广义梯度近似(meta-GGA) (M06-L)、杂化泛函(hyper-GGA)(M06-2X、X3LYP和B3LYP)及其长程校正泛函LC-DFT(CAM-B3LYP、LC-ωPBE和ωB97X)和色散校正密度泛函(DFT-D)(ωB97X-D 和B97-D), 用多种基函数对15 种不同强度的传统氢键和非传统氢键体系的结合能进行了系统的计算与分析. 并与高精度的CCSD(T)/aug-cc-pVQZ 结果比较发现: 在上述各类泛函中, 对于氢键结合能的计算M06-2X 和ωB97X-D 泛函较为精确与可靠, 且没有必要使用过大的基函数,6-311++G(2d, 2p)或aug-cc-pVDZ 水平的基组就已足够, 各类泛函所计算结合能的基组重叠误差(BSSE)均较小, 除ωB97X和ωB97X-D外, 其它9种泛函不经BSSE校正也能得到同样甚至更准确的结果.

关键词: 密度泛函理论, 氢键, 分子间相互作用, 基函数, 基组重叠误差

Abstract: We investigated eleven exchange-correlation energy density functionals including generalized gradient approximation (GGA) (PBE, PW91), meta-GGA (M06-L), hyper-GGA (M06-2X, B3LYP, X3LYP), LC-DFT methods (CAM-B3LYP, LC-ωPBE, ωB97X), and density functional theory with dispersion corrections (DFT-D) methods (ωB97X-D, B97-D) for their performance in describing systems with conventional and non-conventional hydrogen bonds. After comparing the results using the benchmark CCSD(T)/aug-cc-pVQZ approach we found that the M06-2X and ωB97X-D functionals provided the most accurate and reliable results for the fifteen systems studied in this work with strong, moderate, and weak hydrogen bonds. It is important to employ an appropriate basis set to predict the binding energy of hydrogen bonds for all DFT methods and we found that the basis set of 6-311++G(2d, 2p) or aug-cc-pVDZ is adequate. The effect of the basis set superposition error (BSSE) is relatively small for the DFT methods tested. All the methods except for ωB97X and ωB97X-D were found to produce equally accurate or even more accurate results without BSSE correction.

Key words: Density functional theory, Hydrogen bond, Intermolecular interaction, Basis set, Basis set superposition error

MSC2000: 

  • O641