Investigating New Reactivities Enabled by Polariton Photochemistry
Investigating New Reactivities Enabled by Polariton Photochemistry
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DOI：
10.1021/acs.jpclett.9b01599
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发表时间：
2019-09-19
影响因子：
5.7
通讯作者：
Huo, Pengfei
中科院分区：
文献类型：
--
作者：
Mandal, Arkajit;Huo, Pengfei
我们进行量子动力学模拟，研究新的化学反应，使腔量子电动力学。在光腔中，分子与量子化辐射模之间的量子光-物质相互作用产生了一组电子-光子杂化态，即所谓的极化激元。极化激元态适应了基态和激发态电子的曲率，通过利用光-物质相互作用的固有量子行为，开辟了控制光化学反应的新可能性。通过量子动力学模拟，我们证明了模型光异构化反应的选择性可以通过调节腔模的光子频率或光-物质耦合强度来控制，提供了通过光-物质相互作用操纵化学反应的新方法。我们进一步研究了通过将量子化辐射模式耦合到多个分子而实现的集体量子效应。我们的研究结果表明，在共振的情况下，光子在分子之间循环，使多个激发态反应，从而有效地发挥催化剂的作用。在非共振的情况下，分子发射和吸收虚光子，通过基本的量子电动力学过程引发激发态反应。量子动力学模拟的结果揭示了极化激元光化学的基本原理，以及利用光子固有量子行为的有前途的反应性。
We perform quantum dynamics simulations to investigate new chemical reactivities enabled by cavity quantum electrodynamics. The quantum light-matter interactions between the molecule and the quantized radiation mode inside an optical cavity create a set of hybridized electronic-photonic states, so-called polaritons. The polaritonic states adapt the curvatures from both the ground and the excited electronic states, opening up new possibilities to control photochemical reactions by exploiting intrinsic quantum behaviors of light-matter interactions. With quantum dynamics simulations, we demonstrate that the selectivity of a model photoisomerization reaction can be controlled by tuning the photon frequency of the cavity mode or the light- matter coupling strength, providing new ways to manipulate chemical reactions via the light-matter interaction. We further investigate collective quantum effects enabled by coupling the quantized radiation mode to multiple molecules. Our results suggest that in the resonance case, a photon is recycled among molecules to enable multiple excited state reactions, thus effectively functioning as a catalyst. In the nonresonance case, molecules emit and absorb virtual photons to initiate excited state reactions through fundamental quantum electrodynamics processes. These results from quantum dynamics simulations reveal basic principles of polariton photochemistry as well as promising reactivities that take advantage of intrinsic quantum behaviors of photons.