物理化学学报 >> 2010, Vol. 26 >> Issue (04): 1043-1050.doi: 10.3866/PKU.WHXB20100432

量子化学及计算化学 上一篇    下一篇

溶剂效应计算中两种积分方法的比较研究

董博, 陈飞武, 韦美菊   

  1. 北京科技大学化学系, 北京 100083
  • 收稿日期:2010-01-04 修回日期:2010-02-05 发布日期:2010-04-02
  • 通讯作者: 陈飞武 E-mail:chenfeiwu@ustb.edu.cn

Comparative Study of Two Integration Methods for Solvation Effect Calculation

DONG Bo, CHEN Fei-Wu, WEI Mei-Ju   

  1. Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, P. R. China
  • Received:2010-01-04 Revised:2010-02-05 Published:2010-04-02
  • Contact: CHEN Fei-Wu E-mail:chenfeiwu@ustb.edu.cn

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摘要：

采用多面体表面模拟溶质空腔, 讨论了溶剂效应计算中近似积分方法和解析积分方法的平行性和收敛性. 我们发现: 对所研究的40个中性分子, 近似方法和解析方法之间的平行性较好; 但是, 对于20个正离子和27个负离子, 当溶质空腔分别为0.002和0.001 a.u.的等电荷密度面时, 近似方法和解析方法之间的平行性较差, 因此, 近似方法的可靠性不一定有保证. 我们还发现当多面体的表面无限趋近空腔的表面时, 不管采用何种多面体序列, 近似方法和解析方法的基态总能量都基本趋向同一极限值.

关键词: 溶剂效应, 近似积分方法, 解析积分方法, 多面体

Abstract:

The parallelism and convergence of the approximate and analytical integration methods on solvation effect calculation were investigated by simulating the solute cavity with polyhedrons. We find that these two methods have excellent parallelismfor the 40 neutral molecules studied. The parallelismis poor for the 27 anions and 20 cations studied as the cavity is the 0.001 and 0.002 a.u. isodensity contours. The accuracy of the approximation method is, therefore, not guaranteed. We also find that despite the type of polyhedron used to simulate the cavity, the ground state electronic energies of the solute molecules calculated by the above two methods converge to nearly the same limit as the faces of the polyhedrons approach infinity.

Key words: Solvation effect, Approximate integration method, Analytical integration method, Polyhedron