高等学校化学学报 ›› 2012, Vol. 33 ›› Issue (08): 1765-1770.doi: 10.3969/j.issn.0251-0790.2012.08.024

• 物理化学 • 上一篇    下一篇

金属离子Na+,Li+及Mg2+与ClO4-和NO3-形成的无水离子缔合物种的从头算量子化学研究

万素琴1, 张一2, 张浩1, 孙家锺1   

  1. 1. 吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春 130021;
    2. 辽宁工程技术大学化工研究院, 葫芦岛 125000
  • 收稿日期:2012-02-23 出版日期:2012-08-10 发布日期:2012-08-10
  • 通讯作者: 张 浩, 男, 博士, 副教授, 主要从事理论化学基础理论及应用研究. E-mail: stringbell@jlu.edu.cn E-mail:stringbell@mail.jlu.edu.cn
  • 基金资助:

    吉林省自然科学基金(批准号: 20101552)和吉林大学自主研究课题项目(批准号: 450060481346)资助.

Ab initio Investigation on Unhydrated Ion-associated Species Between Na+, Li+, Mg2+ Ions and ClO4-, NO3-

WAN Su-Qin1, ZHANG Yi2, ZHANG Hao1, SUN Chia-Chung1   

  1. 1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130021, China;
    2. Research Institute of Chemical Industry, Liaoning Technical University, Huludao 125000, China
  • Received:2012-02-23 Online:2012-08-10 Published:2012-08-10

摘要: 采用量子化学计算方法在B3LYP/6-311++**水平下对Na+, Li+和Mg2+与ClO4-和NO3-形成的离子缔合物种的结构以及ν1-频率进行了研究, 并将结果与SO42-和上述3种阳离子形成的物种进行了对比. 在缔合物种结构方面, 当阳离子数目≤2时, 与SO42-体系相似, ClO4-和NO3-主要与阳离子形成双齿缔合结构, 而当阳离子数目>2时, 特别是具有2个正电荷的Mg2+离子数目较多时, 由于阳离子间的斥力更大, 与阳离子结合能力较弱的ClO4-和NO3-较难与其形成稳定的离子团簇, 而在SO42-体系中, 则易形成单齿缔合结构. 在ν1-频率的变化趋势方面, 3种阴离子形成的缔合物种大体相同, 说明无水离子团簇的频率变化主要受阳离子性质和缔合结构影响. 虽然阴离子性质也有部分影响, 但不占主要地位.

关键词: 量子化学计算, 离子缔合物种, 缔合结构, ν1-频率

Abstract: The structures of ion-associated species between Na+, Li+, Mg2+ ions and ClO4-, NO3- were optimized via ab initio calculations. The influences of the cations to the ν1-frequencies were also investigated and compared with those in SO42- system. For the ion-associated structures, when the numbers of metal ions are not more than 2, the systems of ClO4- and NO3- are analogous to the SO42- system. That is, the bidentate associated structures are easy to form between the anions and cations. When the numbers of metal ions are more than 2, especially for the clusters with more Mg2+ ion which has more positive charge, the repulsions between metal ions will make the clusters instable in the ClO4- and NO3- systems, while more monodentate structures will form in the SO42- system. The influences of metal ions to the ν1-frequencies of all three anions are similar, which can confirm the changes of frequencies in unhydrated clusters are less influenced by the characteristic of anion but more by the polarization of cation and associated structures.

Key words: Quantum chemical computation, Ion-associated species, Associated structure, ν1-Frequency

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