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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (19): 1986-1990. 上一篇    下一篇

研究论文

α-双环-HMX晶体中二聚作用的理论研究

陈天娜*,1,2，汤业朋2，肖鹤鸣*,1   

  1. (1南京理工大学化工学院分子与材料计算研究所 南京 210094)
    (2中国工程物理研究院化工材料研究所 绵阳 621900)
  • 投稿日期:2009-10-17 修回日期:2010-03-04 发布日期:2010-05-13
  • 通讯作者: 肖鹤鸣 E-mail:xiao@mail.njust.edu.cn
  • 基金资助:

    国家自然科学基金(No. 10576061)资助项目

A Theoretical Study on the Dimerization of α-Bicyclo-HMX

Chen Tianna*,1,2 Tang Yepeng2 Xiao Heming*,1   

  1. (1 Department of Chemistry, Nanjing University of Science and Technology, Nanjing 210094)
    (2 Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900)
  • Received:2009-10-17 Revised:2010-03-04 Published:2010-05-13

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在四种(分别为HF/6-31G*, MP2/6-31G*, B3LYP/6-31G*和PBE1PBE/6-31G*)水平下, 用超分子方法(SM)求得α-双环-HMX(四硝基四氮杂双环辛烷)三种二聚体(I, II和III)中的分子间相互作用能. 用对称性匹配微扰理论(SAPT)与密度泛函理论(DFT)相结合的方法[SAPT(DFT)方法]求得该三种二聚体的分子间相互作用能及其分量. 在四种SM方法中, 以MP2求得的相互作用最强, 但均弱于SAPT(DFT)的计算结果. SM和SAPT(DFT)两种方法求得的相互作用, 均为 I＞III＞II, 归因于三者的分子质心平衡间距(Re) 6.58 ? (I)＜6.95 ? (III)＜8.60 ? (II). 考察SAPT(DFT)方法求得的各作用能分量是I＞III＞II. 密度泛函方法对色散能计算的丢失使其求得的相互作用偏小.

关键词: 四硝基四氮杂双环辛烷(双环-HMX), 分子间作用, 对称性匹配微扰理论, 密度泛函理论

The intermolecular interactions of three tetranitrotetraazabicyclooctane (bicyclo-HMX) dimers have been calculated by Supermolecular Method (SM) based on HF, MP2, B3LYP and PBE1 calculation with 6-31G* basis set. The interaction energies and their components are derived by symmetry- adapted perturbation theory (SAPT) combining density functional theory (DFT). Although the interactions calculated by MP2 are stronger than those that obtained by the other three SM methods, all of them are less than . Intermolecular interaction of the three dimers show decreasing sequences I＞III＞II because their intermolecular separations at equilibrium geometry show the reverse order 6.58 ? (I)＜6.95 ? (III)＜8.60 ? (II). The interaction energy is lower due to the lost of dispersion calculated by DFT method.

Key words: tetranitrotetraazabicyclooctane (bicyclo-HMX), intermolecular interaction, symmetry-adapted perturbation theory, density functional theory