Exact States and Spectra of Vibrationally Dressed Polaritons

Zeb, M. Ahsan; Kirton, Peter; Keeling, Jonathan

doi:10.1021/acsphotonics.7b00916

Cited by 97 publications

(117 citation statements)

References 62 publications

Supporting

Mentioning

114

Contrasting

Order By: Relevance

“…Among these results, the development of the Holstein-Tavis-Cummings (HTC) model of vibronic polaritons [75,134] has been particularly useful, as it has been successfully used to explain features in the optical signals of organic microcavities that were notoriously confusing, such as the apparent breakdown of reciprocity in the oscillator strengths in absorption and emission strengths over specific frequencies [88,195]. Further predictions of the HTC model regarding the nature of the lower polariton manifold were later confirmed using variational techniques [196,197], and applied in subsequent work on singlet fission [198] and long-range energy transfer [158].…”

Section: B Recent Theoretical Progressmentioning

confidence: 98%

Molecular polaritons for controlling chemistry with quantum optics

Herrera

Owrutsky

2020

The Journal of Chemical Physics

240

236

View full text Add to dashboard Cite

This is a tutorial-style introduction to the field of molecular polaritons. We describe the basic physical principles and consequences of strong light-matter coupling common to molecular ensembles embedded in UV-visible or infrared cavities. Using a microscopic quantum electrodynamics formulation, we discuss the competition between the collective cooperative dipolar response of a molecular ensemble and local dynamical processes that molecules typically undergo, including chemical reactions. We highlight some of the observable consequences of this competition between local and collective effects in linear transmission spectroscopy, including the formal equivalence between quantum mechanical theory and the classical transfer matrix method, under specific conditions of molecular density and indistinguishability. We also overview recent experimental and theoretical developments on strong and ultrastrong coupling with electronic and vibrational transitions, with a special focus on cavity-modified chemistry and infrared spectroscopy under vibrational strong coupling. We finally suggest several opportunities for further studies that may lead to novel applications in chemical and electromagnetic sensing, energy conversion, optoelectronics, quantum control and quantum technology.

show abstract

Section: B Recent Theoretical Progressmentioning

confidence: 98%

Molecular polaritons for controlling chemistry with quantum optics

Herrera

Owrutsky

2020

The Journal of Chemical Physics

240

236

View full text Add to dashboard Cite

show abstract

“…Recent theoretical efforts aim at covering this gap by solving a generalized light-electronic-vibrations problem modeled as a Holstein-Tavis-Cummings Hamiltonian. Investigations aim at providing an understanding of the vibrationally induced cavity polariton asymmetry [18,22], vibrationally dressed polaritons [23], dark vibronic polaritons [24,25], developing a cavity Born-Oppenheimer theory [26,27] or deriving relevant simplified models for large scale numerics in the mesoscopic limit [28].…”

mentioning

confidence: 99%

Langevin Approach to Quantum Optics with Molecules

2019

View full text Add to dashboard Cite

We investigate the interaction between light and molecular systems modelled as quantum emitters coupled to a multitude of vibrational modes via a Holstein-type interaction. We follow a quantum Langevin equations approach that allows for analytical derivations of absorption and fluorescence profiles of molecules driven by classical fields or coupled to quantized optical modes. We retrieve analytical expressions for the modification of the radiative emission branching ratio in the Purcell regime and for the asymmetric cavity transmission associated with dissipative cross-talk between upper and lower polaritons in the strong coupling regime. We also characterize the Förster resonance energy transfer process between donor-acceptor molecules mediated by the vacuum or by a cavity mode.PACS numbers: 05.60.Gg, 37.30.+i, 81.05.Fb Recent experimental progress [1] has shown that the Purcell enhancement of the zero-phonon line of a single molecule can strongly alter the branching ratio of spontaneous emission between the line of interest and additional Stokes lines thus turning the molecule into an ideal quantum emitter. At the mesoscopic level, experiments in the collective strong coupling regime of organic molecules with cavities or delocalized plasmonic modes have shown important light-induced modifications of material properties. Experimental and theoretical endeavors go into the direction of charge and energy transport enhancement [2-6], Förster resonance energy transfer (FRET) enhancement [7][8][9][10][11], modified chemical reactivity [12][13][14][15][16], polariton dynamics [17,18] etc. Oftentimes however, experiments rely on theoretical models developed for standard cavity quantum electrodynamics (cavity QED) [19][20][21] with two-level systems where one distinguishes between i) the Purcell regime, characterized by modifications of the spontaneous emission rates and ii) the strong coupling regime leading to the occurrence of hybrid light-matter states referred to as polaritons. Recent theoretical efforts aim at covering this gap by solving a generalized light-electronic-vibrations problem modeled as a Holstein-Tavis-Cummings Hamiltonian. Investigations aim at providing an understanding of the vibrationally induced cavity polariton asymmetry [18,22], vibrationally dressed polaritons [23], dark vibronic polaritons [24,25], developing a cavity Born-Oppenheimer theory [26,27] or deriving relevant simplified models for large scale numerics in the mesoscopic limit [28].We provide here an alternative path based on solving the Holstein-Tavis-Cummings dynamics at the level of operators rather than states. The basic model considers a molecular box (see Fig. 1(b)) comprised of an internal electronic transition coupled to any number of vibrational modes. Radiative decay and vibrational relaxation are included as stochastic source terms in a set of coupled standard quantum Langevin equations [29][30][31][32][33] for vibrational and polaron operators (similarly applied in optomechanical systems [34][35][36]). The method is nu...

show abstract

“…The underlying mechanism that allows a precise determination of the excitation energies of condensed-phase molecular systems is that the polariton appears as a sharp peak in optical spectrum under the inflence of strong coupling between the cavity mode and the electronic excitations of molecules inside the cavity. This is related to the effect of vibronic or polaron decoupling found in the Holstein-Tavis-Cummings (HTC) model that describes molecules with a single vibrational mode that are coupled to an optical cavity [36,[56][57][58][59] and the extended model [60]. However, since the polariton is a collective superposition of a large number of electronic excitations of molecules [see Eq.…”

mentioning

confidence: 99%

Precise determination of excitation energies in condensed-phase molecular systems based on exciton-polariton measurements

Phuc¹,

Ishizaki²

2019

Phys. Rev. Research

View full text Add to dashboard Cite

The precise determination of the excitation energies in condensed-phase molecular systems is important for understanding system-environment interactions as well as for the prerequisite input data of theoretical models used to study the dynamics of the system. The excitation energies are usually determined by fitting of the measured optical spectra that contain broad and unresolved peaks as a result of the thermally random dynamics of the environment. Herein, we propose a method for precise energy determination by strongly coupling the molecular system to an optical cavity and measuring the energy of the resulting polariton. The effect of thermal fluctuations induced by the environment on the polariton is also investigated, from which a power scaling law relating the polariton's linewidth to the number of molecules is obtained. The power exponent gives important information about the environmental dynamics.

show abstract

Exact States and Spectra of Vibrationally Dressed Polaritons

Cited by 97 publications

References 62 publications

Molecular polaritons for controlling chemistry with quantum optics

Molecular polaritons for controlling chemistry with quantum optics

Langevin Approach to Quantum Optics with Molecules

Precise determination of excitation energies in condensed-phase molecular systems based on exciton-polariton measurements

Contact Info

Product

Resources

About