光离子化 BT-1T 阳离子的时间分辨 X 射线吸收光谱理论研究。

Pub Date : 2023-05-26 eCollection Date: 2023-05-01 DOI:10.1063/4.0000183
Anna Kristina Schnack-Petersen, Mátyás Pápai, Sonia Coriani, Klaus Braagaard Møller
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引用次数: 0

摘要

我们从理论上模拟了 BT-1T 阳离子(BT-1T+)的时间分辨 X 射线吸收光谱,以研究该体系的电荷转移反应。我们采用轨迹表面跳跃和量子动力学两种方法来模拟结构随时间的演变和状态群的变化。为了计算基态和激发态的静态 X 射线吸收光谱 (XAS),我们采用了随时间变化的密度泛函理论和耦合簇单双法。两种方法得出的结果非常一致。此外,我们还发现,反应过程中发生的微小结构变化对静态 XAS 的影响很小。 因此,可以根据核动力学模拟确定的状态群和一组静态 XAS 计算,利用基态优化几何来计算 tr-XAS。这种方法可以节省大量计算资源,因为不需要计算所有几何形状的静态光谱。由于 BT-1T 是一种相对坚硬的分子,因此只有在研究弗朗克-康顿点附近的非辐射衰变过程时才应考虑采用概述的方法。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

A theoretical study of the time-resolved x-ray absorption spectrum of the photoionized BT-1T cation.

A theoretical study of the time-resolved x-ray absorption spectrum of the photoionized BT-1T cation.

A theoretical study of the time-resolved x-ray absorption spectrum of the photoionized BT-1T cation.

A theoretical study of the time-resolved x-ray absorption spectrum of the photoionized BT-1T cation.

The time-resolved x-ray absorption spectrum of the BT-1T cation (BT-1T+) is theoretically simulated in order to investigate the charge transfer reaction of the system. We employ both trajectory surface hopping and quantum dynamics to simulate the structural evolution over time and the changes in the state populations. To compute the static x-ray absorption spectra (XAS) of the ground and excited states, we apply both the time-dependent density functional theory and the coupled cluster singles and doubles method. The results obtained are in good agreement between the methods. It is, furthermore, found that the small structural changes that occur during the reaction have little effect on the static XAS. Hence, the tr-XAS can be computed based on the state populations determined from a nuclear dynamics simulation and one set of static XAS calculations, utilizing the ground state optimized geometry. This approach can save considerable computational resources, as the static spectra need not to be calculated for all geometries. As BT-1T is a relatively rigid molecule, the outlined approach should only be considered when investigating non-radiative decay processes in the vicinity of the Franck-Condon point.

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