含能材料生成热的PM6与PM3比较研究(英文)  

Comparative PM6 and PM3 study on heats of formation for high energetic materials

作　　者：龚成章 曾秀琳[1,2] 居学海[1] 

机构地区：[1]南京理工大学化工学院软化学与功能材料教育部重点实验室,江苏南京210094 [2]淮南师范学院化学与化工系,安徽淮南232001

出　　处：《计算机与应用化学》2014年第4期445-450,共6页Computers and Applied Chemistry

基　　金：Supported by the Laboratory of Science and Technology on Combustion and Explosion(9140C3501021101);the Innovation Funding from the Graduate School of NJUST for partial financial~~

摘　　要：用半经验量子化学方法(PM3和PM6)对56种含能材料分子的生成熟进行了计算。与实验结果相比,PM6法预测的生成热的均方根误差为10.62 kcal/mol,而PM3方法的均方根误差为14.06 kcal/mol。PM6方法所产生的平均无符号误差和平均误差均很小于相应的PM3结果。PM3计算结果与实验值的关系为:△_fH_(PM6)=0.9467△_fH_(Expt)+2.919,其线性回归系数R^2为0.9502。该方程可反过来用于校正含能材料的理论计算生成热。经校正后,56种含能材料分子的生成热PM6计算值的均方根误差减小至2.56 kcal/mol。此外,还求得DFT-B3LYP/6-31G*方法与PM6法的生成热计算结果之间的线性关系。当对生成热的精度要求不高时,半经验量子化学PM6法不失为又一种预测生成热的方法之一,特别适合于含能材料分子的高通量筛选。Semi-empirical quantum chemical calculations were used to predict the heats of formation （HOF） of high energetic materials. The predicted heats of formation by PM6 method for 56 high energy materials have a root mean square （rms） deviation of 10.62 kcal/mol, whereas nearly 14.06 kcal/mol was observed using PM3 method in comparison to experimental values. And the AUE and ASE values from PM6 results are much smaller than those of the PM3 results. The relationship between the HOF from the PM6 method and the experimental values was established as： AfHpM6 = 0.9467 △fHEXPT ＋ 2.919, with linear regression coefficient values （R2） being 0.9502. This equation can in return be used to calibrate the theoretical HOF of high energetic materials. After the calibration, the rms for 56 high energy materials from the PM6 results is reduced to 2.56 kcal/mol. In addition, HOF values between the DFT-B3LYP/6-31G＊ and PM6 results have a good linear correlation. Semi-empirical method of PM6 is an alternatively choice for predicting the HOF, especially for the high-throughput screening of high energetic materials when the accuracy of HOF is not a great concern.

关 键 词：生成热 含能材料 PM6 PM3 DFT-B3LYP 线性相关 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O64[理学—物理化学]