多氯代9,10-菲醌的热力学性质及稳定性的理论研究  

Theoretical study on the thermodynamic properties and relative stability of polychlorinated 9,10-phenanthraquinones

作　　者：王雷[1,2] 荣先国[1] 胡威[1] 

机构地区：[1]滨州医学院药学院,山东烟台264003 [2]山东师范大学化学化工与材料科学学院,山东烟台240014

出　　处：《计算机与应用化学》2012年第4期495-498,共4页Computers and Applied Chemistry

基　　金：山东省高校科技计划(J09LC66)

摘　　要：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。The structure optimization and frequency calculation of 135 polychlorinated 9,10-phenanthraquinone compounds were carried out by using density functional theory （DFT） at the B3LYP/6-31G^＊ level and their thermodynamic parameters in the ideal gas state at 298.15 K and 101.3 kPa were obtained. Based on these data, the isodesmic reactions were designed to calculate the standard enthalpy of formation （△FH^θ） and the standard Gibbs free energy of formation （△FG^θ） of PCPQ. Through multiple linear regression analysis, the relationship between thermodynamic parameters and the position and number of chlorine substitution （NPCS） were explored. To our interest, a good dependence can be observed among entropy （S^θ）,△pH^θ, △fG^θ and Npcs. According to the relative magnitude of △fH^θ, the relative stability order of isomers can be decided. Meanwhile, it was found that the chlorine substitution pattern strongly influences the torsional angles （C-C（=O）-C（=O）-C）.

关 键 词：多氯9 10-菲醌 密度泛函理论 热力学性质 相对稳定性 

分 类 号：O642.1[理学—物理化学]