Ultrastrong Coupling of a Single Molecule to a Plasmonic Nanocavity : A First-Principles Study
Kuisma, M., Rousseaux, B., Czajkowski, K. M., Rossi, T. P., Shegai, T., Erhart, P., & Antosiewicz, T. J. (2022). Ultrastrong Coupling of a Single Molecule to a Plasmonic Nanocavity : A First-Principles Study. ACS Photonics, 9(3), 1065-1077. https://doi.org/10.1021/acsphotonics.2c00066
Published inACS Photonics
© 2022 the Authors
Ultrastrong coupling (USC) is a distinct regime of light-matter interaction in which the coupling strength is comparable to the resonance energy of the cavity or emitter. In the USC regime, common approximations to quantum optical Hamiltonians, such as the rotating wave approximation, break down as the ground state of the coupled system gains photonic character due to admixing of vacuum states with higher excited states, leading to ground-state energy changes. USC is usually achieved by collective coherent coupling of many quantum emitters to a single mode cavity, whereas USC with a single molecule remains challenging. Here, we show by time-dependent density functional theory (TDDFT) calculations that a single organic molecule can reach USC with a plasmonic dimer, consisting of a few hundred atoms. In this context, we discuss the capacity of TDDFT to represent strong coupling and its connection to the quantum optical Hamiltonian. We find that USC leads to appreciable ground-state energy modifications accounting for a non-negligible part of the total interaction energy, comparable to kBT at room temperature. ...
PublisherAmerican Chemical Society (ACS)
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Additional information about fundingWe acknowledge financial support from the Swedish Research Council (VR Miljö, Grant No: 2016-06059), the Knut and Alice Wallenberg Foundation (Grant No: 2019.0140), the Polish National Science Center (projects 2019/34/E/ST3/00359 and 2019/35/B/ST5/02477). T.P.R. acknowledges support from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie Grant Agreement No. 838996 and support from the Academy of Finland under the Grant No. 332429. T.J.A. acknowledges support from the Project HPC-EUROPA3 (INFRAIA-2016-1-730897), with the support of the EC Research Innovation Action under the H2020 Programme. ...
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