Gorlaeus Laboratories, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
Chemphyschem. 2009 Dec 21;10(18):3148-73. doi: 10.1002/cphc.200900538.
The absorption properties of chromophores in biomolecular systems are subject to several fine-tuning mechanisms. Specific interactions with the surrounding protein environment often lead to significant changes in the excitation energies, but bulk dielectric effects can also play an important role. Moreover, strong excitonic interactions can occur in systems with several chromophores at close distances. For interpretation purposes, it is often desirable to distinguish different types of environmental effects, such as geometrical, electrostatic, polarization, and response (or differential polarization) effects. Methods that can be applied for theoretical analyses of such effects are reviewed herein, ranging from continuum and point-charge models to explicit quantum chemical subsystem methods for environmental effects. Connections to physical model theories are also outlined. Prototypical applications to optical spectra and excited states of fluorescent proteins, biomolecular photoreceptors, and photosynthetic protein complexes are discussed.
生物分子体系中发色团的吸收性质受到几种微调机制的影响。与周围蛋白质环境的特定相互作用通常会导致激发能的显著变化，但体介电效应也可能起重要作用。此外，在几个发色团近距离的系统中可能会发生强烈的激子相互作用。为了解释的目的，通常希望区分不同类型的环境效应，如几何、静电、极化和响应（或差分极化）效应。本文回顾了可用于分析此类效应的理论方法，范围从连续体和点电荷模型到环境效应的显式量子化学子系统方法。还概述了与物理模型理论的联系。讨论了典型的应用，包括荧光蛋白、生物分子光感受器和光合作用蛋白复合物的光光谱和激发态。
