Cavity-induced modifications of molecular structure in the strong coupling regime

By Javier Galego, F. García-Vidal, J. Feist. 2015

279 citations recorded by the source corpus.

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 ultra-strong coupling regime and show that some molecular observables are affected by the collective coupling strength, while others only depend on the single-molecule coupling constant.

Subfields: Atomic and Molecular Physics, and Optics

View Paper: https://www.semanticscholar.org/paper/0d3f9906a40092e6e1627989050c7e66153d3364

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In Atomic and Molecular Physics, and Optics

1. F. García-Vidal
2. T. Ebbesen
3. J. Feist
4. Javier Galego
5. C. Climent
6. E. Demler
7. C. Ciuti
8. A. Imamoğlu

Citations in the corpus

• Manipulating matter by strong coupling to vacuum fields (2021, background): “These theoretical studies and others (70, 71, 73–80) show that the potential energy surfaces (PES) of the various states at play are modified under strong coupling, which affects conical intersections and internal dynamics, as first pointed out in 2015 (70).”
• Quantum Electrodynamic Control of Matter: Cavity-Enhanced Ferroelectric Phase Transition (2020, background): “[102] J.”
• Roadmap on plasmonics (2018, unknown): “Engineering strong coupling between plasmons and vibrational states of molecules, and further progress in the understanding and control of hot carriers dynamics is beneficial to advance towards optical control of chemical reactions at the nanoscale, an important long-term objective in the field of p”
• Plasmon exciton-polariton lasing (2016, background): “Sufficiently strong-light matter coupling has already been shown to mitigate those effects leading to novel behaviours, such as enhanced exciton transport and conductivity [14–16], in addition to the modification of molecular structures and chemical reactions [17, 18].”
• Exciton-plasmon coupling interactions: from principle to applications (2017, background): “The solution that is considered to be the most promising is cavity-QED [112].”
• Cavity Casimir-Polder Forces and Their Effects in Ground-State Chemical Reactivity (2018, methodology): “to obtain polaritonic PESs [17,28] when performing the Born-Oppenheimer approximation, as successfully used for electronic strong coupling.”