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Electronic relaxation of aqueous aminoazobenzenes studied by time-resolved photoelectron spectroscopy and surface hopping TDDFT dynamics calculations
Faraday Discussions ( IF 3.3 ) Pub Date : 2020-12-21 , DOI: 10.1039/d0fd00111b Evgenii Titov 1 , Johan Hummert 2 , Evgenii Ikonnikov 2 , Roland Mitrić 1 , Oleg Kornilov 2
Faraday Discussions ( IF 3.3 ) Pub Date : 2020-12-21 , DOI: 10.1039/d0fd00111b Evgenii Titov 1 , Johan Hummert 2 , Evgenii Ikonnikov 2 , Roland Mitrić 1 , Oleg Kornilov 2
Affiliation
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Studies of ultrafast relaxation of molecular chromophores are complicated by the fact that most chromophores of biological and technological importance are rather large molecules and are strongly affected by their environment, either solvent or a protein cage. Here we present an approach which allows us to follow transient electronic structure of complex photoexcited molecules. We use the method of time-resolved photoelectron spectroscopy in solution to follow relaxation of two prototypical aqueous chromophores, Methyl Orange and Metanil Yellow, both of which are aminoazobenzene derivatives. Using excitation by 400 nm laser pulses and ionization by wavelength-selected 46.7 nm XUV pulses from high-order harmonic generation we follow relaxation of both molecules via the dark S1 state. The photoelectron spectra yield binding energies of both ground and excited states. We combine the experimental results with surface hopping time-dependent density functional theory (TDDFT) calculations employing B3LYP+D3 and ωB97X−D functionals. The results demonstrate that the method is generally suitable for description of ultrafast dynamics in these molecules and can recover absolute binding energies observed in the experiment. The B3LYP+D3 functional appears to be better suited for these systems, especially in the case of Metanil Yellow, where it indicates the importance of an intramolecular charge transfer state. Our results pave the way towards quantitative understanding of evolving electronic structure in photo-induced relaxation processes.
中文翻译：
时间分辨光电子能谱和表面跳跃TDDFT动力学计算研究了氨基偶氮苯水溶液的电子弛豫
分子发色团的超快弛豫研究由于以下事实而变得复杂：大多数具有生物学和技术重要性的发色团都是相当大的分子，并受其环境（溶剂或蛋白笼）的强烈影响。在这里，我们提出一种方法，使我们能够跟踪复杂的光激发分子的瞬态电子结构。我们在溶液中使用时间分辨光电子能谱法来跟踪两种典型的水性发色团，甲基橙和间甲黄，它们都是氨基偶氮苯衍生物。使用400 nm激光脉冲激发并通过高阶谐波产生的46.7 nm波长选择的XUV脉冲进行电离，我们通过黑暗的S 1跟踪两个分子的弛豫状态。光电子能谱产生基态和激发态的结合能。我们将实验结果与使用B3LYP + D3和ωB97X-D功能的表面跳变时变密度泛函理论（TDDFT）计算相结合。结果表明，该方法通常适合描述这些分子中的超快动力学，并且可以恢复实验中观察到的绝对结合能。B3LYP + D3的功能似乎更适合于这些系统，特别是在偏甲黄的情况下，它表明了分子内电荷转移状态的重要性。我们的研究结果为定量了解光致弛豫过程中不断发展的电子结构铺平了道路。
更新日期：2021-02-15
中文翻译：
时间分辨光电子能谱和表面跳跃TDDFT动力学计算研究了氨基偶氮苯水溶液的电子弛豫
分子发色团的超快弛豫研究由于以下事实而变得复杂：大多数具有生物学和技术重要性的发色团都是相当大的分子，并受其环境（溶剂或蛋白笼）的强烈影响。在这里，我们提出一种方法，使我们能够跟踪复杂的光激发分子的瞬态电子结构。我们在溶液中使用时间分辨光电子能谱法来跟踪两种典型的水性发色团，甲基橙和间甲黄，它们都是氨基偶氮苯衍生物。使用400 nm激光脉冲激发并通过高阶谐波产生的46.7 nm波长选择的XUV脉冲进行电离，我们通过黑暗的S 1跟踪两个分子的弛豫状态。光电子能谱产生基态和激发态的结合能。我们将实验结果与使用B3LYP + D3和ωB97X-D功能的表面跳变时变密度泛函理论（TDDFT）计算相结合。结果表明，该方法通常适合描述这些分子中的超快动力学，并且可以恢复实验中观察到的绝对结合能。B3LYP + D3的功能似乎更适合于这些系统，特别是在偏甲黄的情况下，它表明了分子内电荷转移状态的重要性。我们的研究结果为定量了解光致弛豫过程中不断发展的电子结构铺平了道路。
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