密度泛函方法预测多氯代二苯并-对-二噁英的色谱保留值

Predicting Chromatographic Retention Index of Polychlorinated Dienzo-p-Dioxins with Density Functional Theory(DFT)

运用密度泛函理论方法在B3LYP/6-311G*水平上全优化计算了多氯代二苯并-对-二噁英(PCDDs)系列物的分子结构。基于得到的量子化学参数,分别建立了PCDDs在不同极性色谱柱上的色谱保留指数或相对保留时间的定量结构色谱保留关系(QSRR)模型,其中最低未占据轨道能(ELUMO)对PCDDs的色谱保留行为影响最大。检验结果表明方程相关性显著(R2>0.95)。

Molecular geometries of polychlorinated dibenzo-p--dioxins （PCDDs） were calculated by fully optimization using density functional theory （DFT） at the B3LYP/6--311G＊ level. The obtained quantum chemical parameters were used to establish quantitative structure-retention relationships （QSRRs） for chromatographic retention index （RI） of PCDDs. Energy of the lowest unoccupied molecular orbit （ELUMO） is the main effective factor of all quantum chemical parameters. The QSRR models for various polar columns （DB-5, SE-54, OV-1701） have high correlation （R^2 =0.95）, which show that the models are stable and can be used to predict the chromatographic retention index or the retention time of PCDDs.