DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Molecular Emission near Metal Interfaces: The Polaritonic Regime

Abstract

The strong coupling of a dense layer of molecular excitons with surface-plasmon modes in a metal gives rise to polaritons (hybrid light–matter states) called plexcitons. Surface plasmons cannot directly emit into (or be excited by) free-space photons due to the fact that energy and momentum conservation cannot be simultaneously satisfied in photoluminescence. Most plexcitons are also formally nonemissive, even though they can radiate via molecules upon localization due to disorder and decoherence. However, a fraction of them are bright even in the presence of such deleterious processes. Here in this Letter, we theoretically discuss the superradiant emission properties of these bright plexcitons, which belong to the upper energy branch and reveal huge photoluminescence enhancements compared to bare excitons, due to near-divergences in the density of photonic modes available to them. Our study generalizes the well-known problem of molecular emission next to a metal interface to the polaritonic regime.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Univ. of California, San Diego, CA (United States)
  2. Harvard Univ., Cambridge, MA (United States); Kazan Federal Univ., Kazan (Russia). Inst. of Physics
  3. City Univ. of New York (CUNY), NY (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Excitonics (CE); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); City Univ. of New York (CUNY), NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1566535
Grant/Contract Number:  
SC0001088; SC0017760
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 22; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; solar (photovoltaic); solid state lighting; photosynthesis (natural and artificial); charge transport; optics; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

Yuen-Zhou, Joel, Saikin, Semion K., and Menon, Vinod M. Molecular Emission near Metal Interfaces: The Polaritonic Regime. United States: N. p., 2018. Web. doi:10.1021/acs.jpclett.8b02980.
Yuen-Zhou, Joel, Saikin, Semion K., & Menon, Vinod M. Molecular Emission near Metal Interfaces: The Polaritonic Regime. United States. https://doi.org/10.1021/acs.jpclett.8b02980
Yuen-Zhou, Joel, Saikin, Semion K., and Menon, Vinod M. Mon . "Molecular Emission near Metal Interfaces: The Polaritonic Regime". United States. https://doi.org/10.1021/acs.jpclett.8b02980. https://www.osti.gov/servlets/purl/1566535.
@article{osti_1566535,
title = {Molecular Emission near Metal Interfaces: The Polaritonic Regime},
author = {Yuen-Zhou, Joel and Saikin, Semion K. and Menon, Vinod M.},
abstractNote = {The strong coupling of a dense layer of molecular excitons with surface-plasmon modes in a metal gives rise to polaritons (hybrid light–matter states) called plexcitons. Surface plasmons cannot directly emit into (or be excited by) free-space photons due to the fact that energy and momentum conservation cannot be simultaneously satisfied in photoluminescence. Most plexcitons are also formally nonemissive, even though they can radiate via molecules upon localization due to disorder and decoherence. However, a fraction of them are bright even in the presence of such deleterious processes. Here in this Letter, we theoretically discuss the superradiant emission properties of these bright plexcitons, which belong to the upper energy branch and reveal huge photoluminescence enhancements compared to bare excitons, due to near-divergences in the density of photonic modes available to them. Our study generalizes the well-known problem of molecular emission next to a metal interface to the polaritonic regime.},
doi = {10.1021/acs.jpclett.8b02980},
journal = {Journal of Physical Chemistry Letters},
number = 22,
volume = 9,
place = {United States},
year = {2018},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Influence of a dielectric interface on fluorescence decay time
journal, January 1970


Lifetime of an emitting molecule near a partially reflecting surface
journal, April 1974

  • Chance, R. R.; Prock, A.; Silbey, R.
  • The Journal of Chemical Physics, Vol. 60, Issue 7
  • DOI: 10.1063/1.1681437

Über die Ausbreitung der Wellen in der drahtlosen Telegraphie
journal, January 1909


Theory of Strong Coupling between Quantum Emitters and Propagating Surface Plasmons
journal, March 2013


Strong coupling between surface plasmon polaritons and emitters: a review
journal, December 2014


Strong Coupling between Surface Plasmons and Excitons in an Organic Semiconductor
journal, July 2004


Plexciton Dynamics: Exciton−Plasmon Coupling in a J-Aggregate−Au Nanoshell Complex Provides a Mechanism for Nonlinearity
journal, April 2011

  • Fofang, Nche T.; Grady, Nathaniel K.; Fan, Zhiyuan
  • Nano Letters, Vol. 11, Issue 4
  • DOI: 10.1021/nl104352j

Observation of Selective Plasmon-Exciton Coupling in Nonradiative Energy Transfer: Donor-Selective versus Acceptor-Selective Plexcitons
journal, June 2013

  • Ozel, Tuncay; Hernandez-Martinez, Pedro Ludwig; Mutlugun, Evren
  • Nano Letters, Vol. 13, Issue 7
  • DOI: 10.1021/nl4009106

Surface plasmon resonance mediated photoluminescence properties of nanostructured multicomponent fluorophore systems
journal, January 2014

  • Kochuveedu, Saji Thomas; Kim, Dong Ha
  • Nanoscale, Vol. 6, Issue 10
  • DOI: 10.1039/C4NR00241E

Plexciton Dirac points and topological modes
journal, June 2016

  • Yuen-Zhou, Joel; Saikin, Semion K.; Zhu, Tony
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11783

Strong Coupling between Self-Assembled Molecules and Surface Plasmon Polaritons
journal, November 2017


Quantum Mechanical Description of Raman Scattering from Molecules in Plasmonic Cavities
journal, May 2016

  • Schmidt, Mikolaj K.; Esteban, Ruben; González-Tudela, Alejandro
  • ACS Nano, Vol. 10, Issue 6
  • DOI: 10.1021/acsnano.6b02484

Single-molecule strong coupling at room temperature in plasmonic nanocavities
journal, June 2016

  • Chikkaraddy, Rohit; de Nijs, Bart; Benz, Felix
  • Nature, Vol. 535, Issue 7610
  • DOI: 10.1038/nature17974

Cavity Femtochemistry: Manipulating Nonadiabatic Dynamics at Avoided Crossings
journal, May 2016

  • Kowalewski, Markus; Bennett, Kochise; Mukamel, Shaul
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 11
  • DOI: 10.1021/acs.jpclett.6b00864

Atoms and molecules in cavities, from weak to strong coupling in quantum-electrodynamics (QED) chemistry
journal, March 2017

  • Flick, Johannes; Ruggenthaler, Michael; Appel, Heiko
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 12
  • DOI: 10.1073/pnas.1615509114

Conical Intersections Induced by Quantum Light: Field-Dressed Spectra from the Weak to the Ultrastrong Coupling Regimes
journal, October 2018

  • Szidarovszky, Tamás; Halász, Gábor J.; Császár, Attila G.
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 21
  • DOI: 10.1021/acs.jpclett.8b02609

Hybrid Light–Matter States in a Molecular and Material Science Perspective
journal, October 2016


Cavity-Controlled Chemistry in Molecular Ensembles
journal, June 2016


Suppressing photochemical reactions with quantized light fields
journal, December 2016

  • Galego, Javier; Garcia-Vidal, Francisco J.; Feist, Johannes
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13841

Novel Nanostructures and Materials for Strong Light–Matter Interactions
journal, October 2017


Optics of exciton-plasmon nanomaterials
journal, October 2017

  • Sukharev, Maxim; Nitzan, Abraham
  • Journal of Physics: Condensed Matter, Vol. 29, Issue 44
  • DOI: 10.1088/1361-648X/aa85ef

Polariton chemistry: controlling molecular dynamics with optical cavities
journal, January 2018

  • Ribeiro, Raphael F.; Martínez-Martínez, Luis A.; Du, Matthew
  • Chemical Science, Vol. 9, Issue 30
  • DOI: 10.1039/C8SC01043A

Strong light-matter coupling in quantum chemistry and quantum photonics
journal, September 2018


Coherent Light Harvesting through Strong Coupling to Confined Light
journal, August 2018


Quantum Strong Coupling with Protein Vibrational Modes
journal, October 2016

  • Vergauwe, Robrecht M. A.; George, Jino; Chervy, Thibault
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 20
  • DOI: 10.1021/acs.jpclett.6b01869

Strong Light–Matter Coupling as a New Tool for Molecular and Material Engineering: Quantum Approach
journal, September 2018

  • Kolaric, Branko; Maes, Bjorn; Clays, Koen
  • Advanced Quantum Technologies, Vol. 1, Issue 3
  • DOI: 10.1002/qute.201800001

Energy Transfer between Spatially Separated Entangled Molecules
journal, June 2017

  • Zhong, Xiaolan; Chervy, Thibault; Zhang, Lei
  • Angewandte Chemie International Edition, Vol. 56, Issue 31
  • DOI: 10.1002/anie.201703539

Theory for polariton-assisted remote energy transfer
journal, January 2018

  • Du, Matthew; Martínez-Martínez, Luis A.; Ribeiro, Raphael F.
  • Chemical Science, Vol. 9, Issue 32
  • DOI: 10.1039/C8SC00171E

Organic polaritons enable local vibrations to drive long-range energy transfer
journal, June 2018

  • Sáez-Blázquez, R.; Feist, J.; Fernández-Domínguez, A. I.
  • Physical Review B, Vol. 97, Issue 24
  • DOI: 10.1103/PhysRevB.97.241407

Estimating the conditions for polariton condensation in organic thin-film microcavities
journal, January 2012

  • Bittner, Eric R.; Silva, Carlos
  • The Journal of Chemical Physics, Vol. 136, Issue 3
  • DOI: 10.1063/1.3678015

Polariton condensation with saturable molecules dressed by vibrational modes
journal, February 2014


Nonlinear interactions in an organic polariton condensate
journal, February 2014

  • Daskalakis, K. S.; Maier, S. A.; Murray, R.
  • Nature Materials, Vol. 13, Issue 3
  • DOI: 10.1038/nmat3874

Quantum Symmetry Breaking of Exciton/Polaritons in a Metal-Nanorod Plasmonic Array
journal, February 2016

  • Zaster, Svitlana; Bittner, Eric R.; Piryatinski, Andrei
  • The Journal of Physical Chemistry A, Vol. 120, Issue 19
  • DOI: 10.1021/acs.jpca.5b10726

Coherence in Spontaneous Radiation Processes
journal, January 1954


Superradiance in molecular aggregates
journal, July 1989

  • Spano, Frank C.; Mukamel, Shaul
  • The Journal of Chemical Physics, Vol. 91, Issue 2
  • DOI: 10.1063/1.457174

Spontaneous decay and atomic fluorescence near a metal surface or an absorbing dielectric
journal, February 1988


Electromagnetic interactions of molecules with metal surfaces
journal, November 1984


Fluorescence near interfaces: The role of photonic mode density
journal, April 1998


Spontaneous decay in the presence of dispersing and absorbing bodies: General theory and application to a spherical cavity
journal, October 2000


Macroscopic quantum electrodynamics - Concepts and applications
journal, October 2008

  • Scheel, Stefan; Buhmann, Stefan
  • Acta Physica Slovaca. Reviews and Tutorials, Vol. 58, Issue 5
  • DOI: 10.2478/v10155-010-0092-x

The Occurrence of Singularities in the Elastic Frequency Distribution of a Crystal
journal, March 1953


Radiative lifetime of free excitons in quantum wells
journal, March 1991

  • Andreani, Lucio Claudio; Tassone, Francesco; Bassani, Franco
  • Solid State Communications, Vol. 77, Issue 9
  • DOI: 10.1016/0038-1098(91)90761-J

Photonic analog of a van Hove singularity in metamaterials
journal, July 2013


Measurement of exciton correlations using electrostatic lattices
journal, September 2015


Colloquium : Light scattering by particle and hole arrays
journal, October 2007


Silver nanoparticle array structures that produce remarkably narrow plasmon lineshapes
journal, June 2004

  • Zou, Shengli; Janel, Nicolas; Schatz, George C.
  • The Journal of Chemical Physics, Vol. 120, Issue 23
  • DOI: 10.1063/1.1760740

Anomalous Diffraction Gratings
journal, December 1935


The Theory of Anomalous Diffraction Gratings and of Quasi-Stationary Waves on Metallic Surfaces (Sommerfeld’s Waves)
journal, January 1941


Spontaneous Emission Enhancement of Quantum Dots in a Photonic Crystal Wire
journal, October 2005


Characterization of the Static Disorder in the B850 Band of LH2
journal, July 2001

  • Jang, Seogjoo; Dempster, Sara E.; Silbey, Robert J.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 28
  • DOI: 10.1021/jp010169e

Cavity polaritons in microcavities containing disordered organic semiconductors
journal, February 2003


Room Temperature Polariton Emission from Strongly Coupled Organic Semiconductor Microcavities
journal, April 1999


Modifying Chemical Landscapes by Coupling to Vacuum Fields
journal, January 2012

  • Hutchison, James A.; Schwartz, Tal; Genet, Cyriaque
  • Angewandte Chemie International Edition, Vol. 51, Issue 7
  • DOI: 10.1002/anie.201107033

Ground-State Chemical Reactivity under Vibrational Coupling to the Vacuum Electromagnetic Field
journal, August 2016

  • Thomas, Anoop; George, Jino; Shalabney, Atef
  • Angewandte Chemie, Vol. 128, Issue 38
  • DOI: 10.1002/ange.201605504

Open system perspective on incoherent excitation of light-harvesting systems
journal, September 2017

  • Pachón, Leonardo A.; Botero, Juan D.; Brumer, Paul
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 50, Issue 18
  • DOI: 10.1088/1361-6455/aa8696

Long-Lived Quasistationary Coherences in a V -type System Driven by Incoherent Light
journal, September 2014


Works referencing / citing this record:

Strong light–matter interactions: a new direction within chemistry
journal, January 2019

  • Hertzog, Manuel; Wang, Mao; Mony, Jürgen
  • Chemical Society Reviews, Vol. 48, Issue 3
  • DOI: 10.1039/c8cs00193f

Light-emitting metasurfaces
journal, July 2019

  • Vaskin, Aleksandr; Kolkowski, Radoslaw; Koenderink, A. Femius
  • Nanophotonics, Vol. 8, Issue 7
  • DOI: 10.1515/nanoph-2019-0110

Quantum control with quantum light of molecular nonadiabaticity
journal, November 2019


Manipulating optical nonlinearities of molecular polaritons by delocalization
journal, September 2019