CALCULATIONS ON THE ELECTRONIC STRUCTURE AND UV-VISIBLE SPECTRUM OF OXYHEMOCYANIN
CALCULATIONS ON THE ELECTRONIC STRUCTURE AND UV-VISIBLE SPECTRUM OF OXYHEMOCYANIN
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氧血蓝蛋白电子结构和紫外-可见光谱的计算
DOI：
10.1021/ja971231h
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发表时间：
1999
期刊：
影响因子：
--
通讯作者：
M. Zerner
中科院分区：
文献类型：
--
作者：
G. Estiu;M. Zerner
利用微分重叠模型的中间忽略和多参考组态相互作用研究了氧血蓝蛋白模型的基态电子结构和紫外-可见光谱。实验特征被解释为涉及铜原子的d轨道和过氧化物桥的价轨道的激发，通过它们是反铁磁（AF）耦合。我们的模型，取代组氨酸残基与咪唑，正确地再现了较高的稳定性AF单重态和主要的光谱特征。我们详细研究的几何形状的中心部分的分子，负责的活动，使用实验的电子光谱作为指导。我们进一步研究螯合咪唑的去质子化对预测光谱的影响。中心结构，我们假设最好地再现光谱是非常相似的BLYP密度泛函计算得到的。为了与...
The ground-state electronic structure and UV−visible spectra of models for oxyhemocyanin are examined using the intermediate neglect of differential overlap model and multireference configuration interaction. The experimental features are interpreted as excitations involving the d orbitals of the Cu atoms and the valence orbitals of the peroxide bridge through which they are antiferromagnetically (AF) coupled. Our model, which replaces the histidine residues with imidazoles, reproduces correctly the higher stability of the AF singlet state and the major spectroscopic features. We examine in detail the geometry of the central part of the molecule, responsible for the activity, using the experimental electronic spectrum as a guide. We further examine the effect that deprotonation of the chelating imidazoles has on the predicted spectroscopy. The central structure that we assumed to best reproduce the spectroscopy is very similar to that obtained from BLYP density functional calculations. For comparison with...