Na^+···3,4-二硝基吡唑…H_2O复合物分子间协同效应的理论研究

A theoretical investigation into the cooperativity effect in Na^+…3,4-dinitropyrazole…H_2O complex

为探索3,4-二硝基吡唑高能熔铸炸药中分子…阳离子和阳离子…σ相互作用之间的关系,本论文借助M062X方法,在6-311++G(2d,p)基组水平上研究了Na^+…3,4-二硝基吡唑…H_2O三聚体协同效应,对其进行了分子间相互作用能和协同效应的计算与分析,然后建立了分子间距离R(R_(ternary)-R_(binary))与~2ρ(▽~2ρBCP_(ternary)-▽~2ρBCP_(binary))的线性关系。结果表明,线状三聚体结构中发生了协同效应,而在环状结构中出现了反协同效应。分子间距离R(R_(ternary-)R_(binary))与~2ρ(▽~2ρBCP_(ternary)-▽~2ρBCP_(binary))具有良好的线性关系(R^2=0.992)。AIM(atoms in molecules)与电子云密度转移分析佐证了协同效应的存在。

In order to discover the relationship between the molecule-＂cation and eation＇＂a in the melt-cast explosive involving 3,4-dinitropyrazole, the cooperativity effect in Na＋… 3,4-dinitropyrazole…H2O was investigated by using the M06-2X/6-311 ＋＋G（2d,p） method. Interaction energy and the cooperativity effect were computed and analysed, then established the relationship between the intermolecular distance △R（Rternary-Rbinary） and △2p （△2pBCPternary-V2pBCPbinary）. The result shows that the cooperativity effect appears in the linear conformation while the anti-cooperativity effect is found in the cyclic structure. To our interest, the intermolecular distance △R（gternary-Rbinary） correlates well with △2p （△ZpBCPtemary-△2ρBCPbi,ary）, （R2=0.992）. AIM （atoms in molecules） analysis and electron cloud density analysis confirm the existence of cooperativity.