Ab Initio Simulation of the Ultrafast Circular Dichroism Spectrum of Provitamin D Ring-Opening,The Journal of Physical Chemistry Letters

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Ab Initio Simulation of the Ultrafast Circular Dichroism Spectrum of Provitamin D Ring-Opening
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2023-05-25 , DOI: 10.1021/acs.jpclett.3c00862
Enrico Tapavicza ₁ , Trevor Reutershan ₁ , Travis Thompson ₁

Affiliation

We present a method to simulate ultrafast pump–probe time-resolved circular dichroism (TRCD) spectra based on time-dependent density functional theory trajectory surface hopping. The method is applied to simulate the TRCD spectrum along the photoinduced ring-opening of provitamin D. Simulations reveal that the initial decay of the signal is due to excited state relaxation, forming the rotationally flexible previtamin D. We further show that oscillations in the experimental TRCD spectrum arise from isomerizations between previtamin D rotamers with different chirality, which are associated with the helical conformation of the triene unit. We give a detailed description of the formation dynamics of different rotamers, playing a key role in the natural regulation of vitamin D photosynthesis. Going beyond the sole extraction of decay rates, simulations greatly increase the amount of information that can be retrieved from ultrafast TRCD, making it a sensitive tool to unravel details in the subpicosecond dynamics of photoinduced chirality changes.

中文翻译：

维生素原 D 开环超快圆二色光谱的从头算模拟

我们提出了一种基于时间相关密度泛函理论轨迹表面跳跃来模拟超快泵浦探针时间分辨圆二色性（TRCD）光谱的方法。该方法用于模拟沿着维生素原 D 的光诱导开环的 TRCD 光谱。模拟表明，信号的初始衰减是由于激发态弛豫，形成可旋转的维生素原 D。我们进一步表明，实验中的振荡TRCD 光谱源自具有不同手性的前维生素 D 旋转异构体之间的异构化，这与三烯单元的螺旋构象有关。我们详细描述了不同旋转异构体的形成动力学，这些旋转异构体在维生素 D 光合作用的自然调节中发挥着关键作用。模拟不仅仅只是提取衰减率，还大大增加了从超快 TRCD 中检索的信息量，使其成为揭示光致手性变化的亚皮秒动力学细节的敏感工具。

更新日期：2023-05-25

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