用密度泛函理论研究LAX-112与氟化氢分子间的相互作用  

Interaction between 3,6-Diamino-1,2,4,5-tetrazine-1,4-di-N-oxide and Hydrogen Fluoride by DFT

作　　者：白林[1] 胡银[2] 胡荣祖[2] 宋纪蓉[1,3] 马海霞[1] 

机构地区：[1]西北大学化工学院/陕西省物理无机化学重点实验室,陕西西安710069 [2]西安近代化学研究所,陕西西安710065 [3]故宫博物院文保科技部,北京100009

出　　处：《火炸药学报》2010年第6期19-24,共6页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(21073141);陕西自然科学基金(2009JQ2002);西北大学研究生科研实验(09YSY23)资助项目

摘　　要：在DFT-B3LYP/6-311++G**水平上,计算获得3,6-二氨基-1,2,4,5-四嗪-1,4-二氧化物(LAX-112)与氟化氢(HF)超分子体系势能面上3种全优化几何构型。经基组叠加误差(BSSE)和零点能(ZPE)校正,求得LAX-112与HF分子间的最大相互作用能为-34.41kJ/mol。超分子体系中的电子均由LAX-112向HF转移。用自然键轨道(NBO)分析揭示了分子间的相互作用主要由强氢键所贡献。对优化构型进行了振动频率计算,结果表明,超分子体系中H-X(X=N和F)的伸缩振动频率均发生了大幅度红移。基于统计热力学求得200.0～800.0K温度范围从单体形成二聚体的热力学性质变化,发现二聚过程在较低温度或常温下均能自发进行。Three fully optimized geometries of 3,6-diamino-1,2,4,5-tetrazine-1,4-di-N-oxide/hydrogen fluoride（LAX-112/HF） supermolecule are obtained with density functional theory method（DFT） at the B3LYP/6-311＋＋G＊＊ level.The greatest intermolecular interaction energy of the LAX-112/HF supermolecule obtained with basis set superpositon error（BSSE） correction and zero point energy（ZPE） correction is-34.41 kJ/mol.Electrons in supermolecule systems transfer from LAX-112 to HF.Natural bond orbital（NBO） analysis reveal the origin of the interaction,considering that the interaction energies dominantly contributed by the strong hydrogen bonds.Frequency calculations are carried out on each optimized structure.Vibrational analyses show that there are large red-shifts for H-X（X=N and F） stretching vibrational frequencies in the supermolecule systems.The changes of thermodynamic properties from the monomer to dimer with the temperature ranging from 200.0 K to 800.0 K are obtained using the statistical thermodynamic method.It was found that three LAX-112/HF dimers all can be produced spontaneously from LAX-112 and HF at lower or room temperature.

关 键 词：量子化学 3 6-二氨基-1 2 4 5-四嗪-1 4-二氧化物 氟化氢 分子间相互作用 密度泛函理论 热力学性质 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O626.44[理学—有机化学]