摘要
采用Politzer经验公式,运用密度泛函理论研究了升华焓的预估方法。基于在B3LYP/6–31G**水平上获得56种化合物稳定构型的基础上,运用Multiwfn软件对分子表面进行了定量分析。对比研究了采用Politzer系数和Rice系数对升华焓预估值的影响,结果表明,Politzer系数和Rice系数所造成的最大误差分别为46.1 kJ/mol和38.9 kJ/mol。为了缩小误差,根据34种化合物升华焓的实验值拟合出了一组新的系数(0.000 409(α),2.005 0(β),–2.82(γ)),并用来计算了22种含能化合物的升华焓。计算结果表明,该组新系数使计算值的最大误差为32.6 kJ/mol,标准偏差为13.8 kJ/mol。
Using the Politzer empirical formula, the evaluating method for sublimation enthalpy was investigated by using density functional theory. Based on stable configurations of 56 kinds of compounds obtained at B3LYP/6- 31G＊＊ level, the quantitative analysis on molecular surface was performed by using Multiwfn software. The influence of using Politzer coefficient and using Rice coefficient on the predicted values of sublimation enthalpies was contrasted and investigated. The results show that the maximum errors resulted from Politzer coefficient and Rice coefficient were 46.1 kJ/mol and 38.9 kJ/mol separately. In order to minimize the errors, a team of new coefficients （0.000 409（a）, 2.005 0（β）, -2.82（γ）） were determined according to the experiment values of sublimation enthalpy of 34 kinds of compounds, and the sublimation enthalpies of 22 kinds of energetic compounds were calculated by using these coefficients. The calculated results show that the maximum error of the calculated value resulted from the new coefficient is 32.6 kJ/mol, the standard deviation is 13.8 kJ/mol.
出处
《化学推进剂与高分子材料》
CAS
2014年第1期63-66,共4页
Chemical Propellants & Polymeric Materials
关键词
量子化学
升华焓
理论计算
含能化合物
quantum chemistry
sublimation enthalpy
theoretical calculation
energetic compound
