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Chemistry in Quantum Cavities: Exact Results, the Impact of Thermal Velocities, and Modified Dissociation.
The Journal of Physical Chemistry Letters ( IF 5.7 ) Pub Date : 2020-08-17 , DOI: 10.1021/acs.jpclett.0c01556
Dominik Sidler 1 , Michael Ruggenthaler 1 , Heiko Appel 1 , Angel Rubio 1, 2, 3
Affiliation  

In recent years tremendous progress in the field of light–matter interactions has unveiled that strong coupling to the modes of an optical cavity can alter chemistry even at room temperature. Despite these impressive advances, many fundamental questions of chemistry in cavities remain unanswered. This is also due to a lack of exact results that can be used to validate and benchmark approximate approaches. In this work we provide such reference calculations from exact diagonalization of the Pauli–Fierz Hamiltonian in the long-wavelength limit with an effective cavity mode. This allows us to investigate the reliability of the ubiquitous Jaynes–Cummings model not only for electronic but also for the case of ro-vibrational transitions. We demonstrate how the commonly ignored thermal velocity of charged molecular systems can influence chemical properties while leaving the spectra invariant. Furthermore, we show the emergence of new bound polaritonic states beyond the dissociation energy limit.

中文翻译:

量子腔中的化学:精确的结果,热速度的影响和改进的离解。

近年来,光与物质相互作用领域的巨大进步表明,即使在室温下,与光腔模的强耦合也可以改变化学反应。尽管取得了令人瞩目的进步,但腔体化学的许多基本问题仍未得到解答。这也是由于缺乏可用于验证和基准化近似方法的精确结果。在这项工作中,我们提供了根据Pauli–Fierz哈密顿量在长波长范围内具有有效腔模的精确对角化的参考计算。这使我们能够研究普遍存在的Jaynes-Cummings模型的可靠性,不仅适用于电子形式,还适用于旋转振动过渡的情形。我们证明了带电分子系统通常被忽略的热速度如何影响化学性质而又使光谱不变。此外,我们显示了超过解离能极限的新的束缚极化态的出现。
更新日期:2020-09-18
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