Ultrafast coherent energy transfer Gregory D. Scholes Department of - - PowerPoint PPT Presentation

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Ultrafast coherent energy transfer Gregory D. Scholes Department of - - PowerPoint PPT Presentation

Aug 23, 2023 252 likes •663 views

Ultrafast coherent energy transfer Gregory D. Scholes Department of Chemistry, University of Toronto 1 e group now: Alumni: Collaborators: Yasser Hassan Karyn Ang National Renewable Energy Laboratory Vanessa Huxter Dr. Vitalij

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Ultrafast coherent energy transfer

Gregory D. Scholes

Department of Chemistry, University of Toronto

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Alumni: Karyn Ang

  • Dr. Vitalij Kovalevskij
  • Dr. Peggy Hines
  • Dr. Alexander Doust
  • Dr. Xiujuan Yang
  • Dr. Karolina Fritz
  • Dr. Sree Nair
  • Dr. Sandeep Kumar
  • Dr. Mayrose Salvador
  • Dr. Tieneke Dykstra
  • Dr. Elisabetta Collini
  • Dr. Tihana Mirkovic

Collaborators:

National Renewable Energy Laboratory

Garry Rumbles

Università di Pisa

Benedetta Mennucci

University of New South Wales

Paul Curmi Krystyna Wilk

University of Mons

David Beljonne

University of Houston

Eric Bittner e group now: Yasser Hassan Vanessa Huxter Yaser Khan Anna Lee Shun Lo Michelle Nagy Megan Oh Cathy Wong

  • Dr. John Casey
  • Dr. Carles Curutchet
  • Dr. Jun He
  • Dr. Marcus Jones
  • Dr. Jeongho Kim
  • Dr. Haizheng Zhong

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  • J. Perrin, F. Perrin,

S.I. Vavilov

  • H. Kallmann & F.

London; Ya. Frenkel Vavilov & Galanin Emerson & Arnold

  • Th. Förster

FRET

  • Observed concentration

quenching of dye fluorescence

  • Proposed a quantum

mechanical coupling between donor and acceptor

  • Energy migration depolarizes

fluorescence

  • Spectral overlap condition
  • FRET in biological systems
  • Quantum mechanical coupling

+ spectral overlap 1923–29 1929 1940s 1932 1948

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  • J. Phys. Chem. B 113, 6583–6599 (2009).

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Natural PV: photosynthesis employs specialized energy funnels

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Birstonas, Lithuania September 1996

ESF Workshop (Valkunas and van Grondelle) “... The discovery of these structures has strongly stimulated the analysis of the physical processes responsible for the rapid migration of energy in photosynthesis” “Major questions concern...time over which the excitation must be considered as coherent...”

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Nature, 431, 256–257 (2004).

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Natural nanoscale systems

Elisabetta Collini, Carles, Curutchet, et al. Proceedings from the Paris Research Center Workshop on Energy Flow Dynamics in Biomaterial Systems (2008).

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Light-harvesting in nature

Elisabetta Collini (2008)

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Cryptophyte marine algae

flagella ejectosome gullet periplast

Rhodomonas CS24

Tihana Mirkovic, et al. Photosynthesis Res. (2009).

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Rhodomonas CS24 (a cryptophyte)

Alexander Doust, et al. J. Mol. Biol. (2004)

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Structural model of PC645 (Chroomonas)

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Assign the spectrum to structure

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Assign the spectrum to structure

DBV PCB MBV

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Coherence in cross-peak beats

Ψ+ = 1 √ 2

  • A∗B + AB∗

Ψ− = 1 √ 2

  • A∗B − AB∗

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Electronic beats

= 1 √ 2

  • A∗B + AB∗

= 1 √ 2

  • A∗B − AB∗

A∗, B∗

Ψα=1 = caφa + cbφb + ρα=1

ab

= cac∗

b

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Need information at the amplitude level

population/polarization grating

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τ

T

Two-dimensional photon echo (2DPE)

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Interpreting 2DPE data

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Rephasing vs. non-rephasing signals

Yuan-Chung Cheng & Graham Fleming

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Coherence pathways in the signals

Yuan-Chung Cheng & Graham Fleming

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2DPE signals (real part) decomposed

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2D-2PE (real part) PC645 antenna 293K

from the left top to the right bottom T= 0, 6, 10, 20, 30, 40,50, 70, 80, 90, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 500, 600, 700, 800, 900 fs, 1ps, 2ps, 5ps.

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Electronic beats: rephasing spectra

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Electronic beats

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Electronic beats: rephasing spectra

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Coherence beats (PC645): non-rephasing

2.11 eV 2.185 eV 2.06 eV 2.11 eV 2.185 eV 2.06 eV ~600 cm–1

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Coherence beats (PC645): non-rephasing

2.11 eV 2.185 eV 2.06 eV 2.11 eV 2.185 eV 2.06 eV 2.11 eV 2.185 eV 2.06 eV ~600 cm–1 ~380 cm–1

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Coherently ‘wired’ energy migration

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Quantum probability amplitudes

Classical: P = P(d-a) + P(d1-d2-a) + ... Quantum: P = | G(d-a) + G(d1-d2-a) + ... |2

Time (ps)

  • R. P. Feynman, Rev. Mod. Phys. (1948).

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Weak and strong coupling regimes

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Limits of the dynamics

Förster theory Redfield theory, etc weak electronic coupling strong electronic coupling

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PC645 trajectories: weak coupling to MBV

18.0 17.5 17.0 16.5 16.0 x10

3

10000 8000 6000 4000 2000

  • 0.4
  • 0.3
  • 0.2
  • 0.1

0.0 10000 8000 6000 4000 2000

Energy Time (fs)

Eα=1 Eα=2 Eα=3 Ψα=1 = caφa + cbφb + ccφc ρα=1

ab

= cac∗

b

ρα=1

ab

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SLIDE 34

PC645 trajectories

18.0 17.5 17.0 16.5 16.0 x10

3

10000 8000 6000 4000 2000

  • 0.4
  • 0.3
  • 0.2
  • 0.1

0.0 10000 8000 6000 4000 2000

Energy Time (fs)

ρα=1

ab

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What limits the exciton diffusion length?

ultrafast energy relaxation/transfer

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Energy migration along a PPV chain

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Energy transfer in PPV chains

Jay Singh, Eric Bittner, David Beljonne, GDS (2009).

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Ultrafast anisotropy decay

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Photon echo spectroscopy

population/polarization grating

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Coherence-mediated energy transfer

293 K

Elisabetta Collini & GDS, Science 323, 369–373 (2009). J Phys Chem A 113, 4223–4241 (2009).

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