敌百虫和敌敌畏光谱学特征及发光机制的密度泛函研究  

Density Functional Theory Investigations of the Spectroscopic Characteristics and Luminescent Mechanisms of Dipterex and Dichlorvos

作　　者：李丽清[1,2] 程学礼[1,3] 赵燕云[1] 何国芳[1] 李峰[4] 

机构地区：[1]泰山学院化学化工学院,山东泰安271021 [2]泰山学院科研处,山东泰安271021 [3]山东大学化学化工学院,山东济南270100 [4]泰山学院物理与电子工程学院,山东泰安271021

出　　处：《光谱学与光谱分析》2014年第1期122-127,共6页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(11174215);山东省自然科学基金项目(ZR2012BL03;ZR2012BL10)资助

摘　　要：光谱学方法是检测痕量高毒性有机磷农药的重要手段。利用G09程序包对敌百虫和敌敌畏的基态结构、红外光谱、核磁共振谱、紫外-可见光谱以及激发态结构和荧光/磷光光谱进行研究,从分子轨道角度揭示了其发光实质,为敌百虫和敌敌畏的检测提供理论依据。研究结果表明:(1)敌敌畏和敌百虫IR光谱在1 107cm-1附近有一个较强吸收峰,为P—O键的伸缩振动模式,而敌百虫存在与O—H键有关强吸收峰;(2)敌敌畏的UV-Vis吸收光谱,在182.03nm处有强吸收,而敌百虫在192.42nm处有弱吸收,分别属于ππ*和σπ*跃迁;(3)敌敌畏的发射光谱很弱,且出现双荧光/磷光现象,这可能与敌敌畏基态存在共振结构有关;(4)敌百虫的荧光光谱在1 849.22nm处有一很特别的宽峰,对应S1态LUMO到HOMO的跃迁。By using G09 program package, the ground-state structures, infrared spectra, NMR spectra, UV-Vis spectra as well as the excited structures and fluorescence/pbosphorescence spectra of dipterex and dichlorvos were investigated systematically, and 1 principles were analyzed with the molecular orbitals to provide the theoretical foundation for the detection of trace dipterex and dichlorvos. Our theoretical model revealed that the IR spectra of dipterex and dichlorvos bear strong absorp- tions at about 1 107 cm-1 , which belong to the P--O stretch modes, but dipterex has strong absorption peaks involving the O-H bond; for UV-Vis spectra, dichlorvos has a strong absorption peak at 182. 03 nm, but dipterex has a weak one at 192. 42 nm, which are assigned to ππ＊ and σπ＊ transitions, respectively; the emission spectra of dichlorvos are very weak, and has double fluorescence/phosphorescence characteristics, which may be attributed to the resonance structures of dichlorvos; the fluo- rescence of dipterex has a unique broad peak at 1 849. 22 nm, corresponding to the LUMO→HOMO transition of S1 state.

关 键 词：密度泛函 红外光谱 核磁共振 吸收光谱 荧光 磷光 

分 类 号：O657.3[理学—分析化学]