氮杂杯[2]-间/对-芳烃[2]三嗪与RDX氢键作用理论研究  

Theoretical investigation on the intermolecular hydrogen-bonding interaction between aza-calix[2]-m/p-arene[2]-triazine and RDX

作　　者：彭涛[1] 史文静[2] 任福德[1] 高建峰[1] 

机构地区：[1]中北大学理学院,山西太原030051 [2]山西医科大学第三医院,山西太原030053

出　　处：《分子科学学报》2014年第3期204-213,共10页Journal of Molecular Science

摘　　要：利用MP2和mPWPW91方法,在6-311G**和6-311++G**基组水平上研究了RDX分别与硝基、氨基和迭氮基取代的氮杂杯[2]-间-芳烃[2]三嗪和氮杂杯[2]-对-芳烃[2]三嗪形成的分子间氢键相互作用,并借助自然键轨道(NBO)和分子中的原子(AIM)理论揭示了氢键的本质.结果表明,氮杂杯[2]-间-芳烃[2]三嗪复合物中氢键主要发生在RDX与三嗪环及其取代基之间;氮杂杯[2]-对-芳烃[2]三嗪复合物中氢键主要发生在RDX与杯芳烃环及其取代基之间.分子间相互作用能在-18.82^-40.62kJ/mol之间;经基组叠加误差(BSSE)校正后,相互作用能顺序为e>f≈b>a>c>d和e′>b′>f′>a′>d′>c′.两类复合物中,氨基取代的复合物分子间氢键强于硝基或叠氮基复合物分子间氢键,氨基氮杂杯[2]-对-芳烃[2]三嗪与RDX形成的氢键最强,有望作为降低火炸药感度、进行火炸药废水处理的候选物.为获得稳定性较强的RDX-氨基氮杂杯芳烃超分子炸药,应该选取介电常数较大的溶剂.Intermolecular hydrogen-bonded interactions between RDX and aza-calix[2]-m-arene[2]-triazine or aza-calix[2]-p-arene[2]-triazine with the nitro-,amido-or azide-group have been investigated using the MP2 and mPWPW91 methods at 6-311G＊＊and 6-311＋＋G＊＊levels.Natural bond orbital（NBO）and atoms in molecules（AIM）analyses have been performed to reveal the origin of the hydrogen bond.The results indicate that the main hydrogen-bonded interaction is between RDX and triazine ring or its substituent group for the aza-calix[2]-m-arene[2]-triazine complex with RDX,however,in the complex of the aza-calix[2]-p-arene[2]-triazine with RDX,it is mainly between RDX and aromatic ring or its substituent.The intermolecular interactions are within a range of-18.82--40.62kJ/mol,and the binding energy corrected for the basis set superposition error（BSSE）is in the order of ef≈bacd or e′b′f′a′d′c′.Moreover,for two kinds of complexes,the hydrogenbonded energy in the complex with amido-group is stronger than that in the complex with nitro-,or azide-group.Among these complexes the strongest hydrogen-bonded interaction is found between amido-aza-calix[2]-p-arene[2]-triazine and RDX.Thus,amido-aza-calix[2]-p-arene[2]-triazine can be as the candidate to increase the stability of explosives and eliminate the explosives from waste water.In order to obtain the more stable amido-aza-calixarene supermolecular explosives with RDX,the solvent with greater dielectric constant is necessary.

关 键 词：芳烃[2]三嗪 RDX 分子间氢键 MP2 

分 类 号：O643[理学—物理化学]