论卟吩和其它卟啉衍生物的结构和光谱性质  

Theoretical studies on the structures and electronic absorption spectra of porphine and porphyrin derivatives

作　　者：廖玉婷[1] 饶火瑜[1] 罗新[1] 胡宝群[1] 

机构地区：[1]东华理工大学应用化学系,江西抚州344000

出　　处：《计算机与应用化学》2010年第3期289-297,共9页Computers and Applied Chemistry

基　　金：国家自然科学基金资助项目(40862005);江西省自然科学基金(2007GQH0410);东华理工大学校长基金(DHXK0820)

摘　　要：用TDDFT方法,计算了卟吩的吸收光谱,计算结果与实验较为一致。并使用同样的方法,计算和讨论几种卟啉衍生物的结构和电子吸收光谱。结果发现3种不同的化学修饰方法不仅能改变卟啉中心空穴的大小,而且对卟啉衍生物Q吸收带的影响也各有特点:m位上N原子的掺杂和氢化的方法都大大增加吸收光谱中Q带的吸收强度,而且m位上N原子的掺杂的方法使得2个Q带的极化带吸收峰发生蓝移;但是氢化法却使得Q_x极化带吸收峰蓝移,而Q_y极化带吸收峰红移。另外,O原子取代内环上的—NH的方法对Q带的位置和吸收强度的影响则几乎可以忽略。The correlated ab initio study has been performed on the electronic absorption spectrum of porphine, using time-dependent density functional theory （TDDFT）, and the calculated results are qualitatively in line with the experimental and other calculated re- suits. The calculations also prove that several kinds various chemical modifications to the structure of porphine, such as insertion of aza groups in meso position, substitution of oxygen atoms for --NH, and ring reduction, not only change the size of the central hole, but also affect the electronic absorption spectra. The two chemical modifications of insertion of aza groups in meso positions and hydrogena- tion both significantly intensify the oscillator strengths of the Q band. Insertion of aza groups in meso positions makes the peak positions of two Q component blue-shifted. At the same time, due to hydrogenation, the peak position of the Q, component are red-shifted, and that of the Qy component are blue-shifted. In addition, the effects of substituting O atoms for -NHs in inner core on the peak positions and strenghs of the Q band are nearly negligible.

关 键 词：卟吩 卟啉衍生物 电子吸收光谱 化学修饰 TDDFT 

分 类 号：TQ015.9[化学工程] O6-39[理学—化学]