扩展卟啉(hexaphyrins)及其金配合物结构与电子光谱的理论研究  

Theoretical investigations on geometric structures and UV spectra of hexaphyrins and its metal complexes

作　　者：张盛杰[1] 仇毅翔[1] 王曙光[1] 

机构地区：[1]上海交通大学化学化工学院,上海200240

出　　处：《分子科学学报》2012年第2期95-100,共6页Journal of Molecular Science

基　　金：国家自然科学基金资助项目(20973109)

摘　　要：采用HF、MP2方法和密度泛函理论BP86方法,对扩展卟啉(hexaphyrins)及2个Au+与之组成的双金属配合物的的几何结构、电子结构进行了理论研究,并采用TDDFT方法对2种体系的电子光谱等进行了计算.研究表明hexaphyrins与Au+配位使得体系出现了较为显著的电子相关效应,HF方法不适合该体系的研究,MP2方法和BP86方法给出了相近的几何结构.从简单的卟吩变化到扩展卟啉,体系结构的显著变化导致前线轨道的组成和能级也随之发生复杂的变化,因此很难用简单的四轨道模型对体系所有显著的电子跃迁给予明确的解释.由于Au+与hexaphyrins的配位对体系前线轨道的组成影响不大,因此对hexaphyrins-Au+紫外-可见光谱的计算和解析得到与hexaphyrins相似的结果.Basing on HF,MP2 and DFT BP86 methods,the optimized geometric and electronic structures of hexaphyrin,an expanded porphyrin,and with two Au＋ complexes have been investigated.The UV-Vis spectra of the two systems have been calculated by TDDFT method.The results from the geometric structure difference between MP2,BP86 and HF showed that the coordinating between hexaphyrin and Au＋ brought notable electronic correlation effects.The composition and energy level of frontier molecular orbitals（FMOs） vary complicatedly due to the considerable changing in structures from porphin to expanded porphyrin.It is difficult to explain all the remarkable electronic transitions by orbital model.The UV-Vis result of hexaphyrin-Au＋ is similar with that of hexaphyrin because the coordination had little effects on the composition of FMOs.

关 键 词：扩展卟啉 从头计算 密度泛函理论 电子结构 UV电子光谱 

分 类 号：O641[理学—物理化学]