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在B3LYP/6-31G*水平上对135个多氯代吩噁嗪(PCPXs)系列化合物进行了全优化和振动分析计算,得到各分子在298.15K,1.013×105Pa标准状态下的热力学性质.设计等键反应,计算了PCPXs系列化合物的标准生成热(ΔfH)和标准生成自由能(ΔfG),研究了这些参数与氯原子的取代位置及取代数目(NPCS)之间的关系,结果表明:熵(S)、ΔfH,ΔfG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.以Gaussian03程序的输出文件为基础,采用统计热力学程序计算了PCPXs化合物在200K至1800K的摩尔恒压热容(Cp,m),并用最小二乘法求得Cp,m与温度之间的相关方程,发现Cp,m与T,T-1和T-2之间有着很好的相关性.
The thermodynamic properties of 135 polychlorinated phenoxazine (PCPXs) compounds at B3LYP / 6-31G * level were calculated and analyzed by vibration analysis. The thermodynamic properties of each molecule at 298.15K and 1.013 × 105Pa were obtained. (ΔfH) and standard formation free energy (ΔfG) of PCPXs were calculated. The relationship between these parameters and the substitution position and the number of substitutions of chlorine atoms (NPCS) was studied. The results showed that entropy (S), ΔfH, ΔfG and NPCS have a strong correlation between the generation of free energy based on the relative size of the isomer size, theoretically obtained the relative stability of the isomers to Gaussian03 program output file is (Cp, m) of PCPXs compound at 200K to 1800K were calculated by using the statistical thermodynamic program. The correlation equation between Cp and m and temperature was found by the least square method. It was found that Cp, m and T, There is a good correlation between T-1 and T-2.