氮杂类杯[6]芳烃与HMX分子间相互作用的理论研究  

Theoretical Studies on Intermolecular Interactions between Azacalix[6] arene and HMX

作　　者：张文艳[1] 曹端林[1] 侯素青[1] 王晶[1] 史永文[1] 李科三[1] 刘美峰[1] 谷永龙[1] 

机构地区：[1]中北大学化工与环境学院,山西太原030051

出　　处：《含能材料》2009年第4期436-441,共6页Chinese Journal of Energetic Materials

摘　　要：用密度泛函理论(DFT)B3LYP方法,在6-31G(d)基组水平上,对四种氮杂杯[6]芳烃主体单体(Ma^Md)及其与HMX形成的四种复合体进行了几何构型优化。用自然键轨道(NBO)分析揭示了主客体相互作用的本质。经基组叠加误差(BSSE)和零点能(ZPEC)校正,对四种复合体的相互作用能进行了计算并做了比较。研究发现分子间相互作用能最大的复合物是六氮杂杯[3]-对-三芳烃[3]-2-氨基-1,3,5-三嗪与HMX所形成的复合物,最大相互作用能为-13.98 kJ.mol-1;而且带有取代基的复合物的相互作用能大于没有带取代基的复合物,带有氨基取代基的复合物的相互作用能大于带有硝基取代基的复合物。Four optimized structures of azacalix[6] arene host monomers（ M, - Md ） and their complexes（ a - d） with HMX were obtained at B3LYP/6-31G（d） level. Natural bond orbital（NBO） analysis was performed to reveal the origin of the interaction between hosts and objects. The intermolecular interaction energy was evaluated with basis set superposition error correction（BSSE） and zero point energy correction（ZPEC）. The B3LYP/6-31 G （d） calculations on the four complexes show that the largest interaction energy is - 13.98 kJ · mol^ -1 in the complex composed of HMX and hexaazacalix ~ 3 ]-p-triarene [ 3 ]-2-amido-1,3,5-triazine. Resuhs show that intermolecular interaction energies of azacalix [ 6 ]arenes with substituted groups are stronger than that without substituted groups, and intermolecular interaction energies of azacalix[6 ] arenes with amido groups are stronger than that with nitryl groups.

关 键 词：物理化学 芳烃 分子间相互作用 密度泛函理论(DFT) 分子间氢键 

分 类 号：TQ560.1[化学工程—炸药化工]