用密度泛函理论研究多氯代菲醌的结构和热力学性质

摘要

The structure optimization and frequency calculation of 9, 10-phenanthraquinone (PQ) and 135 polychlorinated PCPQ compounds were conducted using density functional theory (DFT) at the B3LYP/6-31G* level of Gaussian 03 software, and their preferred configurations in the ideal gas state at 298. 15 K and 101. 3 kPa were obtained. Moreover, the values of molar heat capacity of PCPQ compounds at constant pressure (Cp,m) and temperature of 200 — 1 000 K were calculated based on out-put data of Gaussian 03 software, and the linear regression of Cp,m and temperature was conducted with SPSS13. 0. It was found that the chlorine substitution pattern strongly influences the torsional angles C4-C9-C10-C5 of PCPQ compounds. Besides, there is very good relationships between Cp,m and temperature (T, T-1 , T-2) for PCPQ compounds.%使用Gaussian 03程序,采用密度泛函理论(DFT)在B3LYP/6 31G*水平上对136个多氯代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298.15 K、101.3 kPa状态下的优势构型.结合Gaussian 03程序的输出文件,计算了PCPQ化合物在200 K至1000 K的摩尔恒压热容(Cp.m).用SPSS13.0对Cp.m与温度进行多元线性回归.结果表明:氯原子取代模式对PCPQ化合物的扭角A(C4-C9-C10-C5)有很大的影响；与此同时,Cp.m与T,T-1和T-2之间有着很好的相关性(r2＝1.00).