Optical Cavity Manipulation and Nonlinear UV Molecular Spectroscopy of Conical Intersections in Pyrazine
Optical Cavity Manipulation and Nonlinear UV Molecular Spectroscopy of Conical Intersections in Pyrazine
复制标题
吡嗪圆锥形相交的光腔操纵和非线性紫外分子光谱
DOI：
10.1021/jacs.2c00921
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发表时间：
2022
影响因子：
15
通讯作者：
Mukamel, Shaul
中科院分区：
文献类型：
--
作者：
Cho, Daeheum;Gu, Bing;Mukamel, Shaul
光学腔提供了一个多功能的平台，通过强大的光-物质耦合操纵分子的激发态动力学。我们采用光吸收和二维电子光谱模拟研究光腔耦合对光激发吡嗪非绝热动力学的影响。我们观察到了一种新的极化激元圆锥相交（PCI）的出现之间的电子暗态和光子表面的腔频率调谐。PCI可以通过使S2态布居的衰减速率常数加倍来显著改变吡嗪的非绝热动力学。此外，吸收光谱和激发态动力学可以通过调节强的光-物质相互作用来系统地操纵，例如，腔频率和腔耦合强度。我们认为，可调光学腔-分子系统可能为操纵分子的光物理性质提供有前途的方法。
Optical cavities provide a versatile platform for manipulating the excited-state dynamics of molecules via strong light–matter coupling. We employ optical absorption and two-multidimensional electronic spectroscopy simulations to investigate the effect of optical cavity coupling in the nonadiabatic dynamics of photoexcited pyrazine. We observe the emergence of a novel polaritonic conical intersection (PCI) between the electronic dark state and photonic surfaces as the cavity frequency is tuned. The PCI could significantly change the nonadiabatic dynamics of pyrazine by doubling the decay rate constant of the S2state population. Moreover, the absorption spectrum and excited-state dynamics could be systematically manipulated by tuning the strong light–matter interaction, e.g., the cavity frequency and cavity coupling strength. We propose that a tunable optical cavity–molecule system may provide promising approaches for manipulating the photophysical properties of molecules.