硝酸异丙酯水解反应的量子化学计算  

Quantum Chemistry Calculation of Hydrolysis Reaction of Isopropyl Nitrate

作　　者：陈永康 安振涛 陈明华 张力 CHEN Yong-kang;AN Zhen-tao;CHEN Ming-hua;ZHANG Li(Shijiazhuang Campus of Army Engineering University,Shijiazhuang 050003,China;Ordnance Technology Research Institute,Shijiazhuang 050003,China)

机构地区：[1]陆军工程大学石家庄校区,河北石家庄050003 [2]特种勤务研究所,河北石家庄050003

出　　处：《火炸药学报》2018年第5期517-522,共6页Chinese Journal of Explosives & Propellants

基　　金：国防科技项目基金(No.2004053)

摘　　要：研究了硝酸异丙酯的碱性水解反应,计算并比较了4条反应路径;采用从头算MP2/6-311+g(d,p)方法和基组优化反应路径中各驻点的几何结构并计算前线轨道能和振动频率;采用极化连续介质模型研究了反应的溶剂化效应,得到标准态和溶剂化效应下的反应势能面;探讨了pH值变化对水解反应的影响;在CCSD(T)/6-311++g(3df,2p)水平下利用TST、CVT、CVT/ZCT和CVT/SCT方法计算了反应的速率常数。结果表明,在溶剂化条件下,驻点能量降低,反应焓更高;pH值的变化对反应路径顺序影响不大;过渡态能垒为82.72kJ/mol,当能量足够越过能垒时更倾向于生成稳定的异丙醇和水。4种计算方法得到的反应速率常数相对较小,其Arrhenius表达式为:k=1.18×10-23exp(-7 357/T)。The alkaline hydrolysis reaction of isopropyl nitrate was investigated and four reaction pathways were calculated and compared.The geometries of the stationary points in the reaction pathways were optimized using the ab initio MP2/6-311+g(d,p)method and base groups,and the frontier orbital energy and vibration frequencies were calculated.The solvation effect of the reaction was studied by the polarizable continuum model and the reaction potential energy curves under the standard state and the solvent effect was obtained.The influence of pH value on the reaction was discussed.The rate constants of the reaction were calculated by TST,CVT,CVT/ZCT and CVT/SCT method at the CCSD(T)/6-311++g(3df,2p)level.The results show that under the condition of solvation effect,the energy of stationary points are lower and the reaction enthalpy is higher.The change of pH value has little influence on the order of the reaction pathways.The energy barrier is 82.72 kJ/mol,the reaction tends to form stable isopropanol and water when the energy is higher than the barrier.The rate constants of the reaction by the four calculation methods are relatively small,and the Arrhenius expression is k=1.18×10-23exp(-7 357/T).

关 键 词：量子化学 硝酸异丙酯 碱性水解 溶剂化效应 极化连续介质模型 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O641.121[理学—物理化学]