由原子化反应法求算高能化合物的生成热  

Heats of Formation for Energetic Compounds Calculated using Atomization Reactions

作　　者：邱丽美[1,2] 贡雪东[1] 郑剑[2] 肖鹤鸣[1] 

机构地区：[1]南京理工大学化工学院分子与材料计算研究所,江苏南京210094 [2]中国航天科技集团公司四院四十二所,湖北襄樊441003

出　　处：《含能材料》2008年第6期647-651,668,共6页Chinese Journal of Energetic Materials

基　　金：国防科工委973课题(编号:61337);国家博士后科学基金(编号:20070411052)资助项目

摘　　要：基于DFT-B3LYP/6-31G*及HF/6-31G*水平的理论计算结果,借助原子化反应及严格的物理化学公式,对49种已有实验值的高能化合物的生成热进行了计算。与实验值的关联比较表明B3LYP/6-31G*水平的计算结果(x)与实验值(y)之间存在良好的线性关系;对49个标题物,线性方程为y=-75.79+0.98x,相关系数R=0.990,标准偏差SD=28.21。以此线性方法预测了高能化合物的生成热,所得结果与实验值偏差较小,表明B3LYP/6-31G*结合原子化反应是兼顾适用性和可靠性的计算高能化合物生成热的较好方法。基于HF/6-31G*水平的原子化反应法不适于计算高能化合物的生成热。Based on the calculated results at DFT-B3LYP/6-31G^＊ or HF/6-31G^＊ level, heats of formation for 49 energetic compounds were calculated using atomization reactions and physical chemistry equation. By comparing the theoretical and experimental results, a good linear correlation between the experimental heats of formation （y） and the ones calculated at B3LYP/6-31G^＊ level （x） is obtained. For the investigated energetic compounds, the linear equation, the correlative coefficient and the standard deviation are y = - 75.79 ＋ 0. 98x, 0. 990 and 28.21, respectively. Heats of formation obtained by using the linear equation are close to the experimental ones. The results show that by means of atomization reactions and using the results of B3LYP/6-31G^＊ calculation, heats of formation for energetic materials can be obtained. In comparison, the same method based on the results at HF/6-31G^＊ level is not fit for calculating the heats of formation for energetic compounds.

关 键 词：物理化学 生成热 高能化合物 密度泛函理论(DFT) 原子化反应 

分 类 号：TQ560.1[化学工程—炸药化工]