Floquet Study of Quantum Control of the Cis–Trans Photoisomerization of Rhodopsin,Journal of Chemical Theory and Computation

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Floquet Study of Quantum Control of the Cis–Trans Photoisomerization of Rhodopsin
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2018-02-09 00:00:00 , DOI: 10.1021/acs.jctc.7b01217
Pablo E. Videla _{1,

2} , Andreas Markmann _{1,

2} , Victor S. Batista _{1,

2}

Affiliation

Understanding how to control reaction dynamics of polyatomic systems by using ultrafast laser technology is a fundamental challenge of great technological interest. Here, we report a Floquet theoretical study of the effect of light-induced potentials on the ultrafast cis–trans photoisomerization dynamics of rhodopsin. The Floquet Hamiltonian involves an empirical 3-state 25-mode model with frequencies and excited-state gradients parametrized to reproduce the rhodopsin electronic vertical excitation energy, the resonance Raman spectrum, and the photoisomerization time and efficiency as probed by ultrafast spectroscopy. We simulate the excited state relaxation dynamics using the time-dependent self-consistent field method, as described by a 3-state 2-mode nuclear wavepacket coupled to a Gaussian ansatz of 23 vibronic modes. We analyze the reaction time and product yield obtained with pulses of various widths and intensity profiles, defining ’dressed states’ where the perturbational effect of the pulses is naturally decoupled along the different reaction channels. We find pulses that delay the excited-state photoisomerization for hundreds of femtoseconds, and we gain insights on the underlying control mechanisms. The reported findings provide understanding of quantum control, particularly valuable for the development of ultrafast optical switches based on visual pigments.

中文翻译：

视紫红质顺-反光异构化的量子控制研究。

了解如何通过使用超快激光技术控制多原子系统的反应动力学是重大技术兴趣的根本挑战。在这里，我们报告了关于光诱导电位对视紫红质的超快顺式-反式光异构化动力学影响的Floquet理论研究。Floquet Hamiltonian涉及一个经验三态25模式模型，该模型具有参数化的频率和激发态梯度，可再现视紫红质电子垂直激发能，共振拉曼光谱以及通过超快光谱法探测到的光异构化时间和效率。我们使用依赖于时间的自洽场方法来模拟激发态弛豫动力学，方法是将三态2模式核波包耦合到23个振动模式的高斯ansatz来进行描述。我们分析了使用各种宽度和强度分布的脉冲获得的反应时间和产物收率，定义了“修整状态”，其中脉冲的微扰效应沿不同的反应通道自然解耦。我们发现了使激发态光异构化延迟数百飞秒的脉冲，并且我们获得了有关潜在控制机制的见解。报告的发现提供了对量子控制的理解，对于基于视觉颜料的超快速光学开关的开发特别有价值。我们发现了使激发态光异构化延迟数百飞秒的脉冲，并且我们获得了有关潜在控制机制的见解。报告的发现提供了对量子控制的理解，对于基于视觉颜料的超快速光学开关的开发特别有价值。我们发现了使激发态光异构化延迟数百飞秒的脉冲，并且我们获得了有关潜在控制机制的见解。报告的发现提供了对量子控制的理解，对于基于视觉颜料的超快速光学开关的开发特别有价值。

更新日期：2018-02-09

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