物理化学学报 >> 2011, Vol. 27 >> Issue (02): 379-387.doi: 10.3866/PKU.WHXB20110233

理论与计算化学 上一篇    下一篇

Sr2+和Ba2+水分子体系结构和结合能的从头算和ABEEM/MM研究

刘燕1, 王芳芳1,2, 于春阳1, 刘翠1, 宫利东1, 杨忠志1   

  1. 1. 辽宁师范大学化学化工学院, 辽宁 大连 116029;
    2. 济南大学化学化工学院, 济南 250022
  • 收稿日期:2010-10-07 修回日期:2010-12-02 发布日期:2011-01-25
  • 通讯作者: 宫利东 E-mail:gongjw@lnnu.edu.cn
  • 基金资助:

    国家自然科学基金(20633050, 20703022, 21011120087)和辽宁省教育厅基金(2009T057)资助项目

Structures and Binding Energies of Sr2+/Ba2+-Water Systems by Ab initio and ABEEM/MM Method

LIU Yan1, WANG Fang-Fang1,2, YU Chun-Yang1, LIU Cui1, Gong Li-Dong1, YANG Zhong-Zhi1   

  1. 1. School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, Liaoning Province, P. R. China;
    2. School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, P. R. China
  • Received:2010-10-07 Revised:2010-12-02 Published:2011-01-25
  • Contact: Gong Li-Dong E-mail:gongjw@lnnu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20633050, 20703022, 21011120087) and Foundation of Education Bureau of Liaoning Province, China (2009T057).

摘要:

应用从头算方法和ABEEM/MM浮动电荷分子力场, 研究了水合碱土离子团簇Sr2+/Ba2+(H2O)n (n=1-6), 构建了离子-水相互作用的ABEEM/MM势能函数, 获得了水合离子团簇的稳定结构, 计算了结合能. 计算结果表明, ABEEM/MM方法的结果和从头算方法的结果有很好的一致性. 进一步应用ABEEM/MM对Sr2+和Ba2+水溶液进行了分子动力学模拟. 对Sr2+水溶液, 得到的Sr2+-水中氧原子的径向分布函数的第一和第二最高峰分别位于0.257和0.464 nm处, 第一和第二水合层的配位水分子数分别为9.2和11.4; 对Ba2+水溶液, 得到的Ba2+与水中氧原子的径向分布函数的第一和第二最高峰分别位于0.269和0.467 nm处, 第一和第二水合层的配位水分子数分别为9.9和12.4. 这与实验值或其它理论模拟结果有较好的一致性. 对比外层的水分子, 金属离子的极化作用使得溶液中第一水合层中水分子的O―H键长增长, HOH键角减小.

关键词: 水合金属离子团簇, 离子溶剂化, 从头算方法, ABEEM/MM浮动电荷分子力场, 相互作用能

Abstract:

Hydrated clusters of Sr2+/Ba2+(H2O)n (n=1-6) were investigated by the ab initio method and the ABEEM/MM fluctuating charge molecular force field. ABEEM/MM potential functions of cation-water interactions were constructed based on the stable structures and binding energies of the hydrated clusters were obtained. The results from ABEEM/MM are consistent with those from the ab initio method. Furthermore, Sr2+ and Ba2+ aqueous solutions were studied by ABEEM/MM molecular dynamic simulations. Results show that for the Sr2+ aqueous solution the first and second peaks of the SrO radial distribution function (RDF) are located at 0.257 and 0.464 nm, respectively. The coordination numbers of the water molecules for the first and second hydration shells are 9.2 and 11.4, respectively. For the Ba2+ aqueous solution, the first and second peaks of the BaO RDF are located at 0.269 and 0.467 nm, respectively. The coordination numbers of water molecules for the first and second hydration shells are 9.9 and 12.4, respectively. These results also show good consistency with experimental observations and other theoretical simulations. Compared with the external water molecules, the water molecules in the first hydration shell are evidently polarized by the cation and their O―H bond lengths are stretched while the HOH bond angles are found to be reduced.

Key words: Hydrated metal cation cluster, Ion solvation, Ab initio method, ABEEM/MM fluctuating charge molecular force field, Interaction energy

MSC2000: 

  • O641