Polariton chemistry: controlling organic photophysical processes with strong light-matter coupling

Strong coupling (SC) between light and matter has emerged in the last decade as a promising tool to control room-temperature photophysical processes in organic molecules. In this article, we aim to provide a pedagogical introduction to the various flavors of molecular SC involving (a) a single molecule in an optical nanocavity (e.g. a plasmonic junction), and (b) many molecules in an optical microcavity (the collective regime). Although the linear optical properties of these two systems are very similar, their chemical dynamics are drastically different from each another. We will highlight the relevant timescales and rates that can be manipulated via both flavors of SC. We will illustrate these ideas with theoretical and experimental examples from our previous work, which will help us distill the physical mechanisms that are at play in each SC case.

[1]  S. Mukamel,et al.  Novel photochemistry of molecular polaritons in optical cavities. , 2016, Faraday discussions.

[2]  J. Yuen-Zhou,et al.  Polariton Assisted Down-Conversion of Photons via Nonadiabatic Molecular Dynamics: A Molecular Dynamical Casimir Effect. , 2019, The journal of physical chemistry letters.

[3]  F. García-Vidal,et al.  Cavity-induced modifications of molecular structure in the strong coupling regime , 2015, 1506.03331.

[4]  F. W. Cummings,et al.  Approximate Solutions for an N -Molecule-Radiation-Field Hamiltonian , 1969 .

[5]  C. Adachi,et al.  High efficiency thermally activated delayed fluorescence based on 1,3,5-tris(4-(diphenylamino)phenyl)-2,4,6-tricyanobenzene. , 2015, Chemical communications.

[6]  J. Yuen-Zhou,et al.  Triplet harvesting in the polariton regime: a variational polaron approach , 2019, Organic and Hybrid Light Emitting Materials and Devices XXIV.

[7]  Jeremy J. Baumberg,et al.  Single-molecule strong coupling at room temperature in plasmonic nanocavities , 2016, Nature.

[8]  Jonathan Keeling,et al.  Exact states and spectra of vibrationally dressed polaritons , 2016, 1608.08929.

[9]  J. Yuen-Zhou,et al.  Inverting singlet and triplet excited states using strong light-matter coupling , 2019, Science Advances.

[10]  F. Spano,et al.  Theory of Nanoscale Organic Cavities: The Essential Role of Vibration-Photon Dressed States , 2017, 1707.02992.

[11]  Jeremy J. Baumberg,et al.  Single-molecule optomechanics in “picocavities” , 2016, Science.

[12]  V. Menon,et al.  Polariton chemistry: Thinking inside the (photon) box , 2019, Proceedings of the National Academy of Sciences.

[13]  D. Baranov,et al.  Suppression of photo-oxidation of organic chromophores by strong coupling to plasmonic nanoantennas , 2018, Science Advances.

[14]  Jean-Michel Raimond,et al.  Cavity Quantum Electrodynamics , 1993, Quantum Dynamics of Simple Systems.

[15]  F. García-Vidal,et al.  When polarons meet polaritons: Exciton-vibration interactions in organic molecules strongly coupled to confined light fields , 2016, 1608.08019.

[16]  R. Ribeiro,et al.  Polariton chemistry: controlling molecular dynamics with optical cavities , 2018, Chemical science.

[17]  V. Dodonov,et al.  Current status of the dynamical Casimir effect , 2010, 1004.3301.

[18]  T. Ebbesen Hybrid Light-Matter States in a Molecular and Material Science Perspective. , 2016, Accounts of chemical research.

[19]  A. Monkman,et al.  The theory of thermally activated delayed fluorescence for organic light emitting diodes. , 2018, Chemical communications.

[20]  Stephen R. Forrest,et al.  EXCITONIC SINGLET-TRIPLET RATIO IN A SEMICONDUCTING ORGANIC THIN FILM , 1999 .

[21]  J. Gómez Rivas,et al.  Enhanced Delayed Fluorescence in Tetracene Crystals by Strong Light‐Matter Coupling , 2019, Advanced Functional Materials.

[22]  H. Appel,et al.  Cavity Born–Oppenheimer Approximation for Correlated Electron–Nuclear-Photon Systems , 2016, Journal of chemical theory and computation.

[23]  W. Barnes,et al.  Strong coupling between surface plasmon polaritons and emitters: a review , 2014, Reports on progress in physics. Physical Society.

[24]  Zongliang Xie,et al.  Recent advances in organic thermally activated delayed fluorescence materials. , 2017, Chemical Society reviews.

[25]  S. Maier,et al.  Polariton Condensation in Organic Semiconductors , 2017 .

[26]  K. Stranius,et al.  Selective manipulation of electronically excited states through strong light–matter interactions , 2018, Nature Communications.

[27]  M. S. Skolnick,et al.  Strong exciton–photon coupling in an organic semiconductor microcavity , 1998, Nature.