Cavity-Induced Modifications of Molecular Structure in the Strong-Coupling Regime
Cavity-Induced Modifications of Molecular Structure in the Strong-Coupling Regime
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DOI：
10.1103/physrevx.5.041022
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发表时间：
2015-11-09
影响因子：
12.5
通讯作者：
Feist, Johannes
中科院分区：
文献类型：
--
作者：
Galego, Javier;Garcia-Vidal, Francisco J.;Feist, Johannes
在大多数有机分子与腔模的集体强耦合的理论描述中，分子被建模为简单的二能级系统。这幅图未能描述它们内部振转（核）自由度所提供的丰富结构。我们调查的第一性原理模型，充分考虑到电子和核的自由度，允许从一个全新的角度探索强耦合现象。首先，我们证明了玻恩-奥本海默近似在强耦合分子腔结构中的适用性的局限性。对于两个分子的情况下，我们还显示了如何暗态，这在两个级别的图片有效地从腔去耦，确实受到集体强耦合的形成。最后，我们讨论了在超强耦合制度的基态修改，并表明，一些分子的观测值的集体耦合强度的影响，而其他人只依赖于单分子耦合常数。
In most theoretical descriptions of collective strong coupling of organic molecules to a cavity mode, the molecules are modeled as simple two-level systems. This picture fails to describe the rich structure provided by their internal rovibrational (nuclear) degrees of freedom. We investigate a first-principles model that fully takes into account both electronic and nuclear degrees of freedom, allowing an exploration of the phenomenon of strong coupling from an entirely new perspective. First, we demonstrate the limitations of applicability of the Born-Oppenheimer approximation in strongly coupled molecule-cavity structures. For the case of two molecules, we also show how dark states, which within the two-level picture are effectively decoupled from the cavity, are indeed affected by the formation of collective strong coupling. Finally, we discuss ground-state modifications in the ultrastrong-coupling regime and show that some molecular observables are affected by the collective coupling strength, while others depend only on the single-molecule coupling constant.