文献类型：期刊文献

中文题名：间位取代卟啉及其锌卟啉的电子吸收光谱(英文)

英文题名：Electronic Absorption Spectra of Meso-Substituted Porphyrins and Their Zinc Derivatives

作者：曹振锋[1];陈启斌[1];卢运祥[1];刘洪来[1];胡英[1]

机构：[1]华东理工大学,结构可控先进功能材料及其制备教育部重点实验室,上海200237

年份：2012

卷号：28

期号：5

起止页码：1085

中文期刊名：物理化学学报

外文期刊名：Acta Physico-Chimica Sinica

收录：CSTPCD;;Scopus;北大核心:【北大核心2011】；CSCD:【CSCD2011_2012】；PubMed;

基金：The project was supported by the National Natural Science Foundation of China (20806025, 21103047) and National 111 Project of China's Higher Education (B08021).

语种：中文

中文关键词：含时密度泛函理论;电子吸收光谱;电子跃迁;红移;三重激发态

外文关键词：TD-DFT; Electronic absorption spectrum; Electronic transition; Bathochromic shift; Triplet state

摘要：取代的卟啉类衍生物在气敏传感器方面具有广泛的应用前景.本文采用了密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)研究了四种不同取代基的卟啉衍生物(meso位四硝基苯基/四氨基苯基卟啉(NO2PP,NH2PP)及其相应的锌金属卟啉衍生物(NO2ZnPP,NH2ZnPP))的紫外和近紫外光谱特征.利用两种不同的交换相关泛函(广义梯度近似泛函(PBE)和杂化密度泛函(B3LYP))优化了上述四种物质的结构,并应用TD-DFT计算了相应的电子激发能量和振动强度.结果表明,取代卟啉的吸收光谱与大量的电子跃迁有关;与B3LYP泛函预测的光谱相比,PBE泛函所得B带以及Q带的波长位置与实验值更为接近.另外,计算所得硝基取代基卟啉的B带相对于氨基取代基卟啉的B带发生了红移,这与实验现象也保持一致.由于卟啉衍生物的三重激发态在电子转移中有很重要的应用,因此在PBE/6-31G(d)水平上计算了四种物质的最低三重激发态能量,分别为1.426、1.469、1.608和1.581eV.
Meso-substituted porphyrin derivatives have demonstrated great potential as sensing materials for toxic gas detection.In this paper,density functional theory（DFT）and its time-dependent DFT approach（TD-DFT）were employed to investigate the ultraviolet-visible（UV-Vis）or the near-ultraviolet-visible（near-UV-Vis）absorption spectra of meso-tetra（o-nitrophenyl/o-aminophenyl）porphyrins（NO 2 PP,NH 2 PP）and their corresponding zinc derivatives,NO 2 ZnPP and NH 2 ZnPP.The geometry optimizations for these four molecules were obtained from two different exchange-correlation functionals,the generalized-gradient approximation functional PBE（Perdew-Burke-Ernzerhof）and the hybrid functional B3LYP（Becke,three-parameter,Lee-Yang-Parr）.The excitation energies and oscillation strengths were obtained from TD-DFT calculations.Calculations show that the optical absorptions are associated with numerous electronic transitions.In addition,the PBE-predicted wavelengths of the B and Q bands are more consistent with experiment than those predicted by B3LYP.The B band of NO 2-substituted derivative exhibits a bathochromic shift different from that of NH 2-containing material,also consistent with experimental results.In addition,at the PBE/6-31G（d）level of theory,the calculated energies of the lowest triplet excited states of NO 2 PP,NH 2 PP,NO 2 ZnPP,and NH 2 ZnPP are 1.426,1.469,1.608,and 1.581 eV,respectively.