Theoretical study of the excited states of chlorin, bacteriochlorin, pheophytin a and chlorophyll a by the SAC/SAC-CI method

被引:102
作者
Hasegawa, J
Ozeki, Y
Ohkawa, K
Hada, M
Nakatsuji, H [1 ]
机构
[1] Kyoto Univ, Fac Engn, Dept Synthet & Biol Chem, Sakyo Ku, Kyoto 60601, Japan
[2] Inst Fundamental Chem, Sakyo Ku, Kyoto 606, Japan
来源
JOURNAL OF PHYSICAL CHEMISTRY B | 1998年 / 102卷 / 07期
关键词
D O I
10.1021/jp972894o
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Excited states of free base chlorin (FBC), free base Bacteriochlorin (FBBC), pheophytin a (Pheo a), and chlorophyll a (Chlo a), which are derivatives of free base porphine (FBP), were calculated by the SAC (symmetry adapted cluster)/SAC-CI (configuration interaction) method. The results reproduced well the experimentally determined excitation energies. The reduction of the outer double bonds in the porphine ring in the order of FBP, FBC, and FBBC causes a breakdown of the symmetry and a narrowing of the HOMO-LUMO gap, which result in a red shift of the Q(x) band and an increase of its intensity. In the change from Pheo a to Chlo a, the Mg coordination reduces the quasidegeneracy in the Q(x) state and then increases the spectral intensity. The disappearance of the Q(y) humps from the absorption spectrum of Pheo a, compared with that of Chlo a, is due to the red shift of the Q(y) state.
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页码:1320 / 1326
页数:7
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