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采用密度泛函理论(DFT),在B3LYP/6-31G*水平上对135个多氯9,10-菲醌(PCPQ)系列化合物进行全优化和振动分析,得到各分子在298.15K,101.3kPa状态下的热力学参数。设计等键反应,计算了PCPQ系列化合物的标准生成焓(ΔfHθ)和标准生成自由能(ΔfGθ)。用SPSS13.0对这些热力学参数与氯原子的取代位置及取代数目(NPCS)进行多元线性回归,得出相关方程。结果表明:PCPQ系列化合物的Sθ、ΔfHθ和ΔfGθ与NPCS之间有很强的相关性。根据异构体标准生成自由能的相对大小,从理论上求得异构体的相对稳定性。同时,发现氯原子取代模式对扭角(C-C(=O)-C(=O)-C)有很大的影响。
A total of 135 polychlorinated 9,10-phenanthrenequinone (PCPQ) compounds were investigated by density functional theory (DFT) at B3LYP / 6-31G * level. The results showed that all the molecules were at 298.15K, 101.3kPa State of the thermodynamic parameters. The isosteric reaction was designed and the standard enthalpy of formation (ΔfHθ) and standard formation free energy (ΔfGθ) of PCPQ series compounds were calculated. Using SPSS 13.0 multiple linear regression of these thermodynamic parameters and chlorine atom substitution position and the number of substitution (NPCS), the correlation equation was obtained. The results show that there is a strong correlation between Sθ, ΔfHθ and ΔfGθ of PCPQ series compounds and NPCS. According to the relative size of free energy generated by the isomer standard, the relative stability of isomers can be theoretically obtained. In the meantime, it has been found that the chlorine atom substitution pattern has a great influence on the twist angle (C-C (= O) -C (= O) -C).