论文标题
量子腔中的化学：精确的结果，热速度的影响和修饰的解离
Chemistry in Quantum Cavities: Exact Results, the Impact of Thermal Velocities and Modified Dissociation
论文作者
论文摘要
近年来，在光 - 物质相互作用领域的巨大进展已经揭示了，即使在室温下，与光腔模式的强耦合也可以改变化学反应。尽管取得了令人印象深刻的进步，但许多腔中化学的基本问题仍未得到答复。这也是由于缺乏确切的结果，可用于验证和基准近似方法。在这项工作中，我们通过有效的空腔模式在长波长极限的情况下提供了Pauli-Fierz Hamiltonian的确切对角线化的参考计算。这使我们能够研究无处不在的Jaynes-cummings模型的可靠性，不仅是电子的，而且对于RO振动过渡的情况。我们证明了带电分子系统的通常忽略的热速度如何影响化学特性，而光谱不变。此外，我们显示了超出解离能极限的新结合偏极状态的出现。
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 diagonalisation 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.
