Investigation of the S0→S1 excitation in bacteriorhodopsin with the ONIOM(MO:MM) hybrid method

被引:146
作者
Vreven, T
Morokuma, K [1 ]
机构
[1] Emory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
[2] Emory Univ, Dept Chem, Atlanta, GA 30322 USA
[3] Gaussian Inc, N Haven, CT 06473 USA
关键词
opsin shift; bacteriorhodopsin; ONIOM; QM/MM; hybrid methods;
D O I
10.1007/s00214-002-0418-y
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
We have investigated the So and S, electronic states in bacteriorhodopsin using a variety of QM/MM levels. The decomposition of the calculated excitation energies into electronic and electrostatic components shows that the interaction of the chromophore with the protein electric field increases the excitation energy, while polarization effects are negligible. Therefore, the experimentally observed reduction in excitation energy from solution phase to protein environment (the Opsin shift) does not come from the electrostatic interaction with the protein environment, but from either the interaction of the chromophore with the solvent or counter ion, or structural effects. Our high-level ONIOM(TD-B3LYP:Amber) calculation predicts the excitation energy within 8 kcal/mol from experiment, the discrepancy probably being caused by the neglect of polarization of the protein environment. In addition, we have shown that the level of optimization is extremely critical for the calculation of accurate excitation energies in bacteriorhodopsin.
引用
收藏
页码:125 / 132
页数:8
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