Relationship between Excited State Lifetime and Isomerization Quantum Yield in Animal Rhodopsins: Beyond the One-Dimensional Landau–Zener Model,The Journal of Physical Chemistry Letters

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Relationship between Excited State Lifetime and Isomerization Quantum Yield in Animal Rhodopsins: Beyond the One-Dimensional Landau–Zener Model
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2018-05-23 00:00:00 , DOI: 10.1021/acs.jpclett.8b01062
Mohsen M. T. El-Tahawy _{1,

2} , Artur Nenov ₁ , Oliver Weingart ₃ , Massimo Olivucci _{4,

5} , Marco Garavelli ₁

Affiliation

We show that the speed of the chromophore photoisomerization of animal rhodopsins is not a relevant control knob for their light sensitivity. This result is at odds with the momentum-driven tunnelling rationale (i.e., assuming a one-dimensional Landau–Zener model for the decay: Zener, C. Non-Adiabatic Crossing of Energy Levels. Proc. R. Soc. London, Ser. A1932, 137 (833), 696–702) holding that a faster nuclear motion through the conical intersection translates into a higher quantum yield and, thus, light sensitivity. Instead, a model based on the phase-matching of specific excited state vibrational modes should be considered. Using extensive semiclassical hybrid quantum mechanics/molecular mechanics trajectory computations to simulate the photoisomerization of three animal rhodopsin models (visual rhodopsin, squid rhodopsin and human melanopsin), we also demonstrate that phase-matching between three different modes (the reactive carbon and hydrogen twisting coordinates and the bond length alternation mode) is required to achieve high quantum yields. In fact, such “phase-matching” mechanism explains the computational results and provides a tool for the prediction of the photoisomerization outcome in retinal proteins.

中文翻译：

动物视紫红质的激发态寿命与异构化量子产率之间的关系：一维Landau-Zener模型的超越

我们显示动物视紫红质的生色团光异构化的速度不是其光敏性的相关控制旋钮。该结果与动量驱动的隧穿原理（即假设一维Landau-Zener衰减模型）不一致：Zener，C.《能级的绝热交叉》，Proc。R. Soc。London，Ser。一个1932年，137（833），696-702）认为，通过圆锥形相交的更快的核运动转化为更高的量子产率，从而提高了光敏性。相反，应该考虑基于特定激发态振动模式的相位匹配的模型。使用广泛的半经典混合量子力学/分子力学轨迹计算来模拟三种动物视紫红质模型（视觉视紫红质，鱿鱼视紫红质和人黑色素）的光异构化，我们还证明了三种不同模式（活性碳和氢扭曲坐标）之间的相匹配和键长交替模式）是实现高量子产率所必需的。实际上，

更新日期：2018-05-23

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