量子拓扑指数法预测多氯联苯醚的热力学性质  

Prediction of thermodynamic properties of PCDEs with quantum topological indices

作　　者：肖方竹[1] 彭国文[2] 聂长明[1,3] 杨胜园[2,4] 

机构地区：[1]南华大学公共卫生学院,湖南衡阳421001 [2]南华大学化学化工学院,湖南衡阳421001 [3]图卢兹第三大学量子化学与物理实验室,法国图卢兹31077 [4]湖南大学化学生物传感与计量学国家重点实验室,湖南长沙410082

出　　处：《化工学报》2011年第7期1808-1816,共9页CIESC Journal

基　　金：湖南省教育厅科研项目(10C1180);衡阳市科技局项目(2010ks32)

摘　　要：应用密度泛函理论(DFT),在B3LYP/6-31+G(d)基组上优化和振动分析计算了多氯联苯醚(PCDEs)所有209种可能的分子空间几何结构,得到其各原子之间空间拓扑距离,并建立拓扑空间距离矩阵。结合分子中各原子的支化度,应用原子的平衡电负性对分子图进行着色,得到量子拓扑指数PX1、PX2。采用多元线性回归技术建立联苯醚和209种可能结构的多氯联苯醚PCDEs 3种少见报道的热力学性质——标准生成热、标准生成自由能和相对自由能与PX1、PX2的定量关系拓扑模型,并用该模型分别对不同热力学性质进行预测与估算。结果表明,本方法的预测值、估算值与文献[3]的计算值均相吻合。同时,采用留一法(leave-one-out)和外检验方法测试模型的内部稳定性和外部预测能力,测试结果显示模型具有良好的稳定性和较强的预测能力。With density functional theory（DFT）,all 209 possible molecular space structure patterns of polychlorinated diphenyl ethers（PCDEs）were optimized and the frequency was analyzed at the B3LYP/6-31＋G（d）level and the topological distance matrix was built with the space topological distance among atoms.A new group of quantum topological indices PX1 and PX2 was introduced based on the topological distance matrix,and the branch vertex of atoms in a molecule was put forward by coloring atoms in the molecular graph with equilibrium electro-negativity.The seven QSPR models between thermodynamic properties,ΔfH,ΔfGR and ΔfG,and the quantum topological indices PX1 and PX2 of 209 PCDEs were proposed by the multivariate linear regression（MLR）with good stability.The results by the formula indicate that the calculated and predicted data in this study are in good agreement with those in literature and the deviation is within the experimental errors.To validate the estimation reliability for internal samples and the predictive ability for other samples,leave-one-out（LOO）cross validation（CV） and external validation were performed,and the results show that the models are satisfactory.

关 键 词：量子拓扑指数 多氯联苯醚 热力学性质 平衡电负性 拓扑模型 定量结构-性质相关 

分 类 号：O625.15[理学—有机化学]