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Title: Quantum dynamics of a molecular emitter strongly coupled with surface plasmon polaritons: A macroscopic quantum electrodynamics approach

Abstract

In this work, 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.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Princeton Univ., NJ (United States); Academia Sinica, Taipei (Taiwan)
  2. Princeton Univ., NJ (United States)
  3. Academia Sinica, Taipei (Taiwan)
Publication Date:
Research Org.:
Princeton Univ., NJ (United States); Energy Frontier Research Centers (EFRC) (United States). Bioinspired Light-Escalated Chemistry (BioLEC)
Sponsoring Org.:
Academia Sinica; Taiwan Ministry of Science and Technology (MOST); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1612286
Alternate Identifier(s):
OSTI ID: 1530640
Grant/Contract Number:  
SC0015429; MOST 106-2113-M-001-036- MY3
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 1; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; Chemistry; Physics; Nano optics; Green-functions technique; Purcell factor; Surface optics; Quantum electrodynamics; Molecular fluorescence; Open quantum systems; Exciton dynamics; Surface plasmon polaritons

Citation Formats

Wang, Siwei, Scholes, Gregory D., and Hsu, Liang-Yan. Quantum dynamics of a molecular emitter strongly coupled with surface plasmon polaritons: A macroscopic quantum electrodynamics approach. United States: N. p., 2019. Web. https://doi.org/10.1063/1.5100014.
Wang, Siwei, Scholes, Gregory D., & Hsu, Liang-Yan. Quantum dynamics of a molecular emitter strongly coupled with surface plasmon polaritons: A macroscopic quantum electrodynamics approach. United States. https://doi.org/10.1063/1.5100014
Wang, Siwei, Scholes, Gregory D., and Hsu, Liang-Yan. Tue . "Quantum dynamics of a molecular emitter strongly coupled with surface plasmon polaritons: A macroscopic quantum electrodynamics approach". United States. https://doi.org/10.1063/1.5100014. https://www.osti.gov/servlets/purl/1612286.
@article{osti_1612286,
title = {Quantum dynamics of a molecular emitter strongly coupled with surface plasmon polaritons: A macroscopic quantum electrodynamics approach},
author = {Wang, Siwei and Scholes, Gregory D. and Hsu, Liang-Yan},
abstractNote = {In this work, 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.},
doi = {10.1063/1.5100014},
journal = {Journal of Chemical Physics},
number = 1,
volume = 151,
place = {United States},
year = {2019},
month = {7}
}

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Cited by: 5 works
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Works referenced in this record:

Optical Constants of the Noble Metals
journal, December 1972


A single-photon transistor using nanoscale surface plasmons
journal, August 2007

  • Chang, Darrick E.; Sørensen, Anders S.; Demler, Eugene A.
  • Nature Physics, Vol. 3, Issue 11
  • DOI: 10.1038/nphys708

Plasmon-coupled resonance energy transfer: A real-time electrodynamics approach
journal, February 2017

  • Ding, Wendu; Hsu, Liang-Yan; Schatz, George C.
  • The Journal of Chemical Physics, Vol. 146, Issue 6
  • DOI: 10.1063/1.4975815

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


Note on the Numerical Solution of Integro-Differential Equations
journal, February 1967


Extending the applicability of Redfield theories into highly non-Markovian regimes
journal, November 2015

  • Montoya-Castillo, Andrés; Berkelbach, Timothy C.; Reichman, David R.
  • The Journal of Chemical Physics, Vol. 143, Issue 19
  • DOI: 10.1063/1.4935443

Raman spectra of pyridine adsorbed at a silver electrode
journal, May 1974


Effects of Donor–Acceptor Quantum Coherence and Non-Markovian Bath on the Distance Dependence of Resonance Energy Transfer
journal, February 2019


Optical transitions between vibronic states
journal, October 1986


Plasmon-Coupled Resonance Energy Transfer II: Exploring the Peaks and Dips in the Electromagnetic Coupling Factor
journal, September 2018

  • Ding, Wendu; Hsu, Liang-Yan; Heaps, Charles W.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 39
  • DOI: 10.1021/acs.jpcc.8b07210

Ultrafast fluorescent decay induced by metal-mediated dipole–dipole interaction in two-dimensional molecular aggregates
journal, September 2017

  • Hu, Qing; Jin, Dafei; Xiao, Jun
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 38
  • DOI: 10.1073/pnas.1703000114

Characteristic Distance of Resonance Energy Transfer Coupled with Surface Plasmon Polaritons
journal, November 2018

  • Wu, Jhih-Sheng; Lin, Yen-Cheng; Sheu, Yae-Lin
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 24
  • DOI: 10.1021/acs.jpclett.8b03429

Displaced Fock states and their connection to quasiprobabilities
journal, December 1991


Strong coupling in molecular exciton-plasmon Au nanorod array systems
journal, February 2016

  • Fedele, Stefano; Hakami, Manal; Murphy, Antony
  • Applied Physics Letters, Vol. 108, Issue 5
  • DOI: 10.1063/1.4941078

JUNO and neutrinoless double beta decay
journal, November 2015


Theory of multichromophoric coherent resonance energy transfer: A polaronic quantum master equation approach
journal, July 2011

  • Jang, Seogjoo
  • The Journal of Chemical Physics, Vol. 135, Issue 3
  • DOI: 10.1063/1.3608914

Theory of vibronic intensity borrowing. Comparison of Herzberg‐Teller and Born‐Oppenheimer coupling
journal, May 1973

  • Orlandi, G.; Siebrand, W.
  • The Journal of Chemical Physics, Vol. 58, Issue 10
  • DOI: 10.1063/1.1679014

Self-Coupling of a Two-Level System by a Mirror
journal, November 1969


Solutions of integral and integro-differential equation systems by using differential transform method
journal, November 2008


Resonant excitation transfer: A quantum electrodynamical study
journal, April 1987

  • Andrews, David L.; Sherborne, Brad S.
  • The Journal of Chemical Physics, Vol. 86, Issue 7
  • DOI: 10.1063/1.451910

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

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

Effect of surface plasmons on transitions in molecules
journal, March 1975

  • Philpott, Michael R.
  • The Journal of Chemical Physics, Vol. 62, Issue 5
  • DOI: 10.1063/1.430708

Near-Zone Mediation of RET by One and Two Proximal Particles
journal, March 2019


Reversible dynamics of single quantum emitters near metal-dielectric interfaces
journal, January 2014


Control of the absorption of a four-level quantum system near a plasmonic nanostructure
journal, May 2017


Berechnung der nat�rlichen Linienbreite auf Grund der Diracschen Lichttheorie
journal, January 1930

  • Weisskopf, V.; Wigner, E.
  • Zeitschrift f�r Physik, Vol. 63, Issue 1-2
  • DOI: 10.1007/bf01336768

A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
journal, July 2004

  • Yanai, Takeshi; Tew, David P.; Handy, Nicholas C.
  • Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57
  • DOI: 10.1016/j.cplett.2004.06.011

Spontaneous emission interference in negative-refractive-index waveguides
journal, July 2009


Classical Aspects of Energy Transfer in Molecular Systems
journal, July 1970

  • Kuhn, Hans
  • The Journal of Chemical Physics, Vol. 53, Issue 1
  • DOI: 10.1063/1.1673749

Purcell Factor: A Tunable Metric for Plasmon-Coupled Fluorescence Emission Enhancements in Cermet Nanocavities
journal, December 2015

  • Srinivasan, Venkatesh; Ramamurthy, Sai Sathish
  • The Journal of Physical Chemistry C, Vol. 120, Issue 5
  • DOI: 10.1021/acs.jpcc.5b11311

Plasmon-Coupled Resonance Energy Transfer
journal, May 2017

  • Hsu, Liang-Yan; Ding, Wendu; Schatz, George C.
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 10
  • DOI: 10.1021/acs.jpclett.7b00526

Comparison of quantum and semiclassical radiation theories with application to the beam maser
journal, January 1963


Schwingungsstruktur der Elektronenübergänge bei mehratomigen Molekülen
journal, January 1933

  • Herzberg, G.; Teller, E.
  • Zeitschrift für Physikalische Chemie, Vol. 21B, Issue 1
  • DOI: 10.1515/zpch-1933-2136

Generalized effective mode volume for leaky optical cavities
journal, January 2012

  • Kristensen, P. T.; Van Vlack, C.; Hughes, S.
  • Optics Letters, Vol. 37, Issue 10
  • DOI: 10.1364/ol.37.001649

Plasmonics for improved photovoltaic devices
journal, February 2010

  • Atwater, Harry A.; Polman, Albert
  • Nature Materials, Vol. 9, Issue 3, p. 205-213
  • DOI: 10.1038/nmat2629

Increased light harvesting in dye-sensitized solar cells with energy relay dyes
journal, June 2009

  • Hardin, Brian E.; Hoke, Eric T.; Armstrong, Paul B.
  • Nature Photonics, Vol. 3, Issue 7
  • DOI: 10.1038/nphoton.2009.96

A unified theory of radiative and radiationless molecular energy transfer
journal, August 1989


Non-Markovian dynamics in plasmon-induced spontaneous emission interference
journal, February 2017


Three-dimensional quantization of the electromagnetic field in dispersive and absorbing inhomogeneous dielectrics
journal, May 1998


Spectral properties of a strongly coupled quantum-dot–metal-nanoparticle system
journal, May 2014


Lasing action in strongly coupled plasmonic nanocavity arrays
journal, June 2013

  • Zhou, Wei; Dridi, Montacer; Suh, Jae Yong
  • Nature Nanotechnology, Vol. 8, Issue 7
  • DOI: 10.1038/nnano.2013.99

The enhancement of Raman scattering, resonance Raman scattering, and fluorescence from molecules adsorbed on a rough silver surface
journal, May 1983

  • Weitz, D. A.; Garoff, S.; Gersten, J. I.
  • The Journal of Chemical Physics, Vol. 78, Issue 9
  • DOI: 10.1063/1.445486

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


Coherent Coupling of Molecular Excitons to Electronic Polarizations of Noble Metal Nanoparticles
journal, November 2004

  • Wiederrecht, Gary P.; Wurtz, Gregory A.; Hranisavljevic, Jasmina
  • Nano Letters, Vol. 4, Issue 11
  • DOI: 10.1021/nl0488228

The rotating-wave approximation: consistency and applicability from an open quantum system analysis
journal, September 2010

  • Fleming, Chris; Cummings, N. I.; Anastopoulos, Charis
  • Journal of Physics A: Mathematical and Theoretical, Vol. 43, Issue 40
  • DOI: 10.1088/1751-8113/43/40/405304

Plasmonic Purcell factor and coupling efficiency to surface plasmons. Implications for addressing and controlling optical nanosources
journal, August 2016


Intermolecular energy transfer in the presence of dispersing and absorbing media
journal, April 2002


Theory of coherent resonance energy transfer for coherent initial condition
journal, October 2009

  • Jang, Seogjoo
  • The Journal of Chemical Physics, Vol. 131, Issue 16
  • DOI: 10.1063/1.3247899

Quantum interference between decay channels of a three-level atom in a multilayer dielectric medium
journal, June 2001


Electromagnetic theory of enhanced Raman scattering by molecules adsorbed on rough surfaces
journal, October 1980

  • Gersten, Joel; Nitzan, Abraham
  • The Journal of Chemical Physics, Vol. 73, Issue 7
  • DOI: 10.1063/1.440560

Transformation Optics Approach to Plasmon-Exciton Strong Coupling in Nanocavities
journal, August 2016


Lessons from nature about solar light harvesting
journal, September 2011

  • Scholes, Gregory D.; Fleming, Graham R.; Olaya-Castro, Alexandra
  • Nature Chemistry, Vol. 3, Issue 10
  • DOI: 10.1038/nchem.1145

Nanoscale imaging and spontaneous emission control with a single nano-positioned quantum dot
journal, February 2013

  • Ropp, Chad; Cummins, Zachary; Nah, Sanghee
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2477

Study of the Franck-Condon and Herzberg-Teller Approximations
journal, October 1974

  • Lin, S. H.; Eyring, H.
  • Proceedings of the National Academy of Sciences, Vol. 71, Issue 10
  • DOI: 10.1073/pnas.71.10.3802

Review Label-free detection with high-Q microcavities: a review of biosensing mechanisms for integrated devices
journal, January 2012


Increased light harvesting in dye-sensitized solar cells with energy relay dyes
journal, November 2009


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    • The Journal of Chemical Physics, Vol. 152, Issue 2
    • DOI: 10.1063/1.5142731