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arXiv:2112.09554

Picocavity-controlled Sub-nanometer Resolved Single Molecule Non-linear Fluorescence

Lyu, Siyuan, Yuan Zhang, Yao Zhang, Kainan Chang, Guangchao Zheng, Luxia Wang

Published Dec 17, 2021• 0 citations
arXivHTMLPDF

Abstract

In this article, we address fluorescence of single molecule inside a plasmonic picocavity by proposing a semi-classical theory via combining the macroscopic quantum electrodynamics theory and the open quantum system theory. To gain insights into the experimental results [Nat. Photonics, 14, 693 (2020)], we have further equipped this theory with the classical electromagnetic simulation of the pico-cavity, formed by single atom decorated silver STM tip and a silver substrate, and the time-dependent density functional theory calculation of zinc phthalocyanine molecule. Our simulations not only reproduce the fluorescence spectrum as measured in the experiment, confirming the influence of extreme field confinement afforded by the picocavity, but also reveal Rabi oscillation dynamics and Mollow triplets spectrum for moderate laser excitation. Thus, our study highlights the possibility of coherently manipulating the molecular state and exploring non-linear optical phenomena with the plasmonic picocavity.

DOI
10.48550/arxiv.2112.09554

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In this article, we address fluorescence of single molecule inside a plasmonic picocavity by proposing a semi-classical theory via combining the macroscopic quantum electrodynamics theory and the open quantum system theory. To gain insights into the experimental results [Nat. Photonics, 14, 693 (2020)], we have further equipped this theory with the classical electromagnetic simulation of the pico-cavity, formed by single atom decorated silver STM tip and a silver substrate, and the time-dependent density functional theory calculation of zinc phthalocyanine molecule. Our simulations not only reproduce the fluorescence spectrum as measured in the experiment, confirming the influence of extreme field confinement afforded by the picocavity, but also reveal Rabi oscillation dynamics and Mollow triplets spectrum for moderate laser excitation. Thus, our study highlights the possibility of coherently manipulating the molecular state and exploring non-linear optical phenomena with the plasmonic picocavity.
Strong coupling with single molecules in plasmonic picocavities has emerged as a resource for room-temperature quantum control with nanoscale light. Tip-based nanoprobes can measure the local dynamics of individual molecular picocavities, but the overhead associated with sampling an inhomogeneous picocavity distribution can be challenging for scalability. We propose a macroscopic approach in which an ensemble of molecular picocavities acts as a nonlinear plasmonic metamaterial. Using a quantum optics perspective, we study theoretical performance limits for optical cross-phase modulation in the system, taking into account realistic distributions of picocavity volumes and molecular transition frequencies. The medium nonlinearity is mediated by local strong coupling with the lowest vibronic emission sideband of individual organic chomophores. The local vacua change the refractive index of the medium at the frequency of a weak probe field ωp\omega_pωp​, set to drive the bare zero-phonon absorption band. Refractive index variations Δn/n\Delta n/nΔn/n of a few percent, relative to a molecule-free scenario, are feasible with dilute ensembles. The probe phase evolution can be switched off in the presence of a signal field at a higher frequency ωs\omega_sωs​, for intensities as low as 10 kW/cm2^22. The mechanism for optical switching involves a novel (ωp+ωs\omega_p+\omega_sωp​+ωs​) two-photon absorption channel, assisted by local vacuum fields. Our work paves the way for future studies of plasmonic metamaterials that exploit strong light-molecule interactions, for applications in optical state preparation and control.
We propose to use molecular picocavity ensembles as macroscopic coherent nonlinear optical devices enabled by nanoscale strong coupling. For a generic picocavity model that includes molecular and photonic disorder, we derive theoretical performance bounds for coherent cross-phase modulation signals using weak classical fields of different frequencies. We show that strong coupling of the picocavity vacua with a specific vibronic sideband in the molecular emission spectrum results in a significant variation of the effective refractive index of the metamaterial relative to a molecule-free scenario due to a vacuum-induced Autler–Townes effect. For a realistic molecular disorder model, we demonstrate that cross-phase modulation of optical fields as weak as 10 kW/cm2 is feasible using dilute ensembles of molecular picocavities at room temperature, provided that the confined vacuum is not resonantly driven by the external probe field. Our work paves the way for the development of plasmonic metamaterials that exploit strong coupling for optical state preparation and quantum control.
We study a molecular emitter above a silver surface in the framework of macroscopic quantum electrodynamics and explore the population dynamics including non-Markovian effects. The theory we present is general for molecular fluorescence in the presence of dielectrics with any space-dependent, frequency-dependent, or complex dielectric functions. Furthermore, the proposed theory allows us to calculate the memory kernel of polaritons using computational electrodynamics packages. In the limit of a high vibration frequency, the different strengths of exciton-polariton couplings lead to distinct characteristics in the population dynamics, e.g., Franck-Condon-Rabi oscillation. (The frequency of Rabi oscillation is dependent on the Franck-Condon factor.) Additionally, in a specific condition, we derive a parameter-free formula that can be used to estimate the exciton-polariton coupling between a molecular emitter and a nanocavity, and the coupling estimated by our theory is in good agreement with the reported experimental results [Chikkaraddy et al., Nature 535, 127-130 (2016)].
In this study, we present the superradiance effects of N identical molecular emitters inside Fabry–Pérot (FP) cavity systems in the framework of macroscopic quantum electrodynamics. The proposed theory can estimate the enhancement of spontaneous emission rates, including the effects of cavity geometry and material dielectric properties. Moreover, our study connects the multichromophoric excitation energy transfer theory and the Tavis–Cummings model via identical cooperative decay rates and dipole–dipole shifts. For molecules resonant with the cavity photon mode, we find that the enhancement is not exactly proportional to N even in a perfect FP cavity due to the effects of electrostatic dipole–dipole interactions. Moreover, in a silver FP cavity, our simulation shows that the enhancement saturates for a large N, indicating that the cavity photon mode can lead to only the collective emission of a limited number of molecules. For molecules in the proximity of the silver mirror, we demonstrate that under specific conditions, the subradiance of molecular emitters can occur through surface plasmon polaritons. Our study not only provides new insights into the mechanism of superradiance effects but also demonstrates that collective effects such as superradiance and subradiance can be controlled by manipulating the dielectric environments.
The resonance fluorescence of a two-level single molecular system interacting with a plasmonic nanostructure is investigated. Specific regions of space are identified, where a balance exists between the near-field enhancement and the modification of the decay rate, such that the fluorescence spectrum of the molecule exhibits the Mollow triplet and the emission photons are antibunched. The utilization of such quantum phenomena at the vicinity of custom-designed plasmonic nanostructures paves the way for applications in nanoscale quantum devices and quantum information processing.
Abstract Interactions between a single emitter and cavity provide the archetypical system for fundamental quantum electrodynamics. Here we show that a single molecule of Atto647 aligned using DNA origami interacts coherently with a sub-wavelength plasmonic nanocavity, approaching the cooperative regime even at room temperature. Power-dependent pulsed excitation reveals Rabi oscillations, arising from the coupling of the oscillating electric field between the ground and excited states. The observed single-molecule fluorescent emission is split into two modes resulting from anti-crossing with the plasmonic mode, indicating the molecule is strongly coupled to the cavity. The second-order correlation function of the photon emission statistics is found to be pump wavelength dependent, varying from g (2) (0) = 0.4 to 1.45, highlighting the influence of vibrational relaxation on the Jaynes-Cummings ladder. Our results show that cavity quantum electrodynamic effects can be observed in molecular systems at ambient conditions, opening significant potential for device applications.