Quantum dynamical effects of vibrational strong coupling in chemical reactivity.
Quantum dynamical effects of vibrational strong coupling in chemical reactivity.
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DOI：
10.1038/s41467-023-38368-x
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发表时间：
2023-05-12
影响因子：
16.6
通讯作者：
Reichman, David R.
中科院分区：
文献类型：
--
作者：
Lindoy, Lachlan P.;Mandal, Arkajit;Reichman, David R.
最近的实验表明，基态化学反应性可以修改时，将分子系统内的红外腔，分子振动强烈耦合到电磁辐射。这种现象缺乏可靠的理论解释。在这里，我们采用了一个精确的量子动力学方法来研究模型的腔修改的化学反应在凝聚相。该模型包含的反应坐标的通用溶剂的耦合，腔耦合到反应坐标或非反应模式，和腔的耦合损耗模式。因此，许多最重要的功能，需要逼真的造型腔修改化学反应。我们发现，当一个分子耦合到一个光学腔，它是必不可少的量子力学处理的问题，以获得反应性的变化的定量帐户。我们发现了与量子力学状态分裂和共振相关的速率常数的巨大而急剧的变化。从我们的模拟中出现的功能更接近那些在实验中观察到的比以前的计算，即使是现实的耦合和腔损耗的小值。这项工作突出了振动极化激元化学的全量子处理的重要性。实验表明，将分子置于红外腔中会改变它们的反应性，这种效应缺乏明确的理论解释。在这里，作者表明，理解这一过程的关键可能在于量子光-物质相互作用。
Recent experiments suggest that ground state chemical reactivity can be modified when placing molecular systems inside infrared cavities where molecular vibrations are strongly coupled to electromagnetic radiation. This phenomenon lacks a firm theoretical explanation. Here, we employ an exact quantum dynamics approach to investigate a model of cavity-modified chemical reactions in the condensed phase. The model contains the coupling of the reaction coordinate to a generic solvent, cavity coupling to either the reaction coordinate or a non-reactive mode, and the coupling of the cavity to lossy modes. Thus, many of the most important features needed for realistic modeling of the cavity modification of chemical reactions are included. We find that when a molecule is coupled to an optical cavity it is essential to treat the problem quantum mechanically to obtain a quantitative account of alterations to reactivity. We find sizable and sharp changes in the rate constant that are associated with quantum mechanical state splittings and resonances. The features that emerge from our simulations are closer to those observed in experiments than are previous calculations, even for realistically small values of coupling and cavity loss. This work highlights the importance of a fully quantum treatment of vibrational polariton chemistry. Experiments suggest that placing molecules in an infrared cavity alters their reactivity, an effect lacking a clear theoretical explanation. Here, the authors show that the key to understanding this process may lie in quantum light-matter interactions.
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影响因子：
4.4
作者：
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通讯作者：
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影响因子：
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作者：
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