Molecular polaritonics in dense mesoscopic disordered ensembles

Sommer, Christian; Reitz, Michael; Mineo, Francesca; Genes, Claudiu

doi:10.1103/physrevresearch.3.033141

Cited by 27 publications

(26 citation statements)

References 49 publications

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“…This observation could constitute the basis for an effective theory as developed in Ref. [38], which allows for the derivation of an effective unidirectional Markovian loss dynamics for the symmetric operator.…”

Section: This Is Based On the Orthonormality Conditionmentioning

confidence: 84%

Cooperative subwavelength molecular quantum emitter arrays

Holzinger,

Oh,

Reitz

et al. 2022

Preprint

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Dipole-coupled subwavelength quantum emitter arrays respond cooperatively to external light fields as they may host collective delocalized excitations (a form of excitons) with super-or subradiant character. Deeply subwavelength separations typically occur in molecular ensembles, where in addition to photon-electron interactions, electron-vibron couplings and vibrational relaxation processes play an important role. We provide analytical and numerical results on the modification of super-and subradiance in molecular rings of dipoles including excitations of the vibrational degrees of freedom. While vibrations are typically considered detrimental to coherent dynamics, we show that molecular dimers or rings can be operated as platforms for the preparation of long-lived dark superposition states aided by vibrational relaxation. In closed ring configurations, we extend previous predictions for the generation of coherent light from ideal quantum emitters to molecular emitters, quantifying the role of vibronic coupling onto the output intensity and coherence.

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Section: This Is Based On the Orthonormality Conditionmentioning

confidence: 84%

Cooperative subwavelength molecular quantum emitter arrays

Holzinger,

Oh,

Reitz

et al. 2022

Preprint

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“… 142 Instead, the strongly delocalized electromagnetic field in the cavity opens up long-range interaction channels in a disordered ensemble of molecules. 143 This makes it highly challenging to infer photochemical properties of an ensemble of N molecules from the detailed study of a very restricted subset of it. To take into account the large number of emitters, one approach is to use strongly simplified molecular models, such as the Holstein model where each molecule is described by two displaced harmonic oscillators describing nuclear motion in the electronic ground and excited states.…”

Section: Theoretical Approaches and Challengesmentioning

confidence: 99%

Theoretical Challenges in Polaritonic Chemistry

2022

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Polaritonic chemistry exploits strong light–matter coupling between molecules and confined electromagnetic field modes to enable new chemical reactivities. In systems displaying this functionality, the choice of the cavity determines both the confinement of the electromagnetic field and the number of molecules that are involved in the process. While in wavelength-scale optical cavities the light–matter interaction is ruled by collective effects, plasmonic subwavelength nanocavities allow even single molecules to reach strong coupling. Due to these very distinct situations, a multiscale theoretical toolbox is then required to explore the rich phenomenology of polaritonic chemistry. Within this framework, each component of the system (molecules and electromagnetic modes) needs to be treated in sufficient detail to obtain reliable results. Starting from the very general aspects of light–molecule interactions in typical experimental setups, we underline the basic concepts that should be taken into account when operating in this new area of research. Building on these considerations, we then provide a map of the theoretical tools already available to tackle chemical applications of molecular polaritons at different scales. Throughout the discussion, we draw attention to both the successes and the challenges still ahead in the theoretical description of polaritonic chemistry.

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“…z)P (E 1 )...P (E N ), (10) where P (E j ) is the disorder distribution function of E j . When evaluating G X,Y (z), N j=1 g 2 z+iEj → Π(z) in Eq.…”

Section: Thermodynamic Limit and Effective Hamiltonianmentioning

confidence: 99%

“…These states are denoted as 'dark states' and 'dark state reservoir' in the literature. Bright and dark states are theoretically understood accurately for homogeneous systems without disorder, while the nature of these states in the presence of disorder is still under debate [6][7][8][9][10][11][12][13][14][15][16][17]. * jianshu@mit.edu Specifically, disorder leads to a mixing of the dark states and the light field, such that they can contribute to spectroscopy and transport.…”

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confidence: 99%

Unusual Dynamical Properties of Disordered Polaritons in Micocavities

Engelhardt,

Cao

2021

Preprint

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The strong light-matter interaction in microcavities gives rise to intriguing phenomena, such as cavity-mediated transport that can potentially overcome the Anderson localization. Yet, an accurate theoretical treatment is challenging as the matter (e.g., molecules) are subject to large energetic disorder. In this article, we develop the Green's function solution to the Fano-Anderson model and use the exact analytical solution to quantify the effects of energetic disorder on the spectral and transport properties in microcavities. Starting from microscopic equation of motions, we derive an effective non-Hermitian Hamiltonian and predict a set of scaling laws: (i) The complex eigen-energies of the effective Hamiltonian exhibit an exceptional point, which leads to underdamped coherent dynamics in the weak disorder regime, where the decay rate increases with disorder, and overdamped incoherent dynamics in the strong disorder regime, where the slow decay rate decreases with disorder. (ii) The total density of states of disordered ensembles can be exactly partitioned into the cavity, bright-state and dark-state local density of states, which are determined by the complex eigen solutions and can be measured via spectroscopy. (iii) The cavity-mediated relaxation and transport dynamics are intimately related such that the energy-resolved relaxation and transport rates are proportional to the cavity local density of states. The ratio of the disorder averaged relaxation and transport rates equals the molecule number, which can be interpreted as a result of a quantum random walk. (iv) A turnover in the rates as a function of disorder or molecule density can be explained in terms of the overlap of the disorder distribution function and the cavity local density of states. These findings reveal the significant impact of the dark states on the local density of states and consequently their crucial role in optimizing spectroscopic and transport properties of disordered ensembles in cavities. I. INTRODUCTION.

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Molecular polaritonics in dense mesoscopic disordered ensembles

Cited by 27 publications

References 49 publications

Cooperative subwavelength molecular quantum emitter arrays

Cooperative subwavelength molecular quantum emitter arrays

Theoretical Challenges in Polaritonic Chemistry

Unusual Dynamical Properties of Disordered Polaritons in Micocavities

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