A Modified Resonance-Theoretic Framework for Structure−Property Relationships in a Halochromic Oxonol Dye
A Modified Resonance-Theoretic Framework for Structure−Property Relationships in a Halochromic Oxonol Dye
复制标题
卤代 Oxonol 染料结构-性能关系的改进共振理论框架
DOI：
10.1021/ct100001b
复制
发表时间：
2010
影响因子：
5.5
通讯作者：
S. Olsen
中科院分区：
文献类型：
--
作者：
S. Olsen
我证明了对共振色理论的修正(以Brooker(Rev.Mod.)太棒了。1942、14、275)和Platt(J.Chem.太棒了。1956，25，80))提供了一个精确的框架，用于合理化绿色荧光蛋白(GFP)发色团(一种不对称的氧酚染料)的质子化状态的从头算激发能。我认为共振理论中使用的原始模型空间(特别是一对Lewis结构)与该理论的一个核心方面(特别是激发能与末端环的基团特定碱性(Brooker碱性)之间的关系)在形式上是不一致的。我认为一个更合适的模型空间应该由一个基于群定域轨道的完整的活动空间ansatz组成。然后，我证明了状态平均完全活动空间自洽场(SA-CASSCF)问题的解正好是这种形式。这一系列SA-CASSCF解决方案为我们提供了一个客观严谨的基础。
I demonstrate that a modification of the resonance color theory (in its form advocated by Brooker (Rev. Mod. Phys. 1942, 14, 275) and by Platt (J. Chem. Phys. 1956, 25, 80)) provides an accurate framework for rationalizing the ab initio excitation energies of the protonation states of the green fluorescent protein (GFP) chromophore (an asymmetric oxonol dye). I suggest that the original model space used in the resonance theory (specifically, a pair of Lewis structures) is formally inconsistent with a core aspect of the theory (specifically, a relationship between excitation energies and group-specific basicities (Brooker basicities) of the terminal rings). I argue that a more appropriate model space would consist of a complete active space ansatz based on group-localized orbitals. I then show that there is a solution to the state-averaged complete active space self consistent field (SA-CASSCF) problem with exactly this form. This family of SA-CASSCF solutions provides an objectively rigorous foundation fo...