摘要
为了探究目前常用的3种辅助方法(原子化能、原子当量和等键反应方法)计算的生成热(HOF)值的精确性,首先在B3LYP/6-311G(d,p)理论水平下对160种新型含能分子做了结构优化和频率计算,在MP2/6-311++G(d,p)理论水平下对分子进行单点能计算;分别读取热力学数值与电子能量后利用3种常用的辅助方法(原子化能方法、等键反应方法和原子当量方法)计算HOF值,与G4(MP2)-6X方法结合原子化能方法计算的HOF值进行回归分析,分别拟合了其相关系数;建立了线性回归方程,可采用该方程结合B3LYP/6-311G(d,p)//MP2/6-311++G(d,p)理论水平获得G4(MP2)-6X方法的计算精度;计算了160个物质在不同理论水平和生成焓计算方法下的生成焓。结果表明,3种方法的相关性为:原子化能方法>等键反应方法>原子当量方法。
To investigate the accuracy of the currently used three auxiliary methods(atomization energy,equivalent bonding and isodesmic reaction methods)for calculating the heat of formation(HOF)values,the structure optimization and frequency calculations were performed for 160 kinds of novel energetic molecules at the B3LYP/6-311G(d,p)theoretical level.The molecules were subject to single-point energy calculations at the MP2/6-311++G(d,p)theoretical level.The HOF values were calculated using the three commonly used auxiliary reactions(atomization energy method,equivalent bonding method,and atom equivalent method)by extracting thermodynamic values and electronic energies,where the results were compared with the HOF values directly output by the G4(MP2)-6X method,and the regression coefficients were fitted for each method.The linear regression equation was established,which can be used in combination with B3LYP/6-311G(d,p)//MP2/6-311++G(d,p)theoretical level to obtain the calculation accuracy of G4(MP2)-6X method.The enthalpies of formation of 160 kinds of substances at different theoretical levels and enthalpies of formation calculation methods were calculated.The correlation of the three methods was found to be:atomization energy method>equivalent bonding method>atom equivalent method.
作者
刘玥
易平平
林晨晨
刘超
易小艺
何飘
LIU Yue;YI Ping-ping;LIN Chen-chen;LIU Chao;YI Xiao-yi;HE Piao(College of Chemistry and Chemical Engineering,Central South University,Changsha 410083,China)
出处
《火炸药学报》
EI
CAS
CSCD
北大核心
2023年第11期971-983,I0004,共14页
Chinese Journal of Explosives & Propellants
基金
国家自然科学基金(No.22005345)
爆炸科学与技术国家重点实验室(北京理工大学)开放课题(No.KFJJ23-14M)。
