ELEC2017 - Karyn Ross - Teaching and Learning Lean in Services
Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of...
Transcript of Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of...
![Page 1: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/1.jpg)
Ultrafast coherent energy transfer
Gregory D. ScholesDepartment of Chemistry, University of Toronto
1
![Page 2: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/2.jpg)
Alumni:
Karyn AngDr. Vitalij KovalevskijDr. Peggy HinesDr. Alexander DoustDr. Xiujuan YangDr. Karolina FritzDr. Sree NairDr. Sandeep KumarDr. Mayrose SalvadorDr. Tieneke DykstraDr. Elisabetta ColliniDr. Tihana Mirkovic
Collaborators:
National Renewable Energy LaboratoryGarry Rumbles
Università di PisaBenedetta Mennucci
University of New South WalesPaul CurmiKrystyna Wilk
University of MonsDavid Beljonne
University of HoustonEric Bittner
e group now:
Yasser HassanVanessa HuxterYaser KhanAnna LeeShun LoMichelle NagyMegan OhCathy Wong
Dr. John CaseyDr. Carles CurutchetDr. Jun HeDr. Marcus JonesDr. Jeongho KimDr. Haizheng Zhong
2
![Page 3: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/3.jpg)
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
3
![Page 4: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/4.jpg)
J. Phys. Chem. B 113, 6583–6599 (2009).
4
![Page 5: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/5.jpg)
Natural PV: photosynthesisemploys specialized energy
funnels
5
![Page 6: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/6.jpg)
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...”
6
![Page 7: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/7.jpg)
Nature, 431, 256–257 (2004).
7
![Page 8: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/8.jpg)
Natural nanoscale systems
Elisabetta Collini, Carles, Curutchet, et al. Proceedings from the Paris Research Center Workshop on Energy Flow Dynamics in Biomaterial Systems (2008).
8
![Page 9: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/9.jpg)
Light-harvesting in nature
Elisabetta Collini (2008)
9
![Page 10: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/10.jpg)
Cryptophyte marine algae
flagella
ejectosome
gullet
periplast
Rhodomonas CS24
Tihana Mirkovic, et al. Photosynthesis Res. (2009).
10
![Page 11: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/11.jpg)
Rhodomonas CS24 (a cryptophyte)
Alexander Doust, et al. J. Mol. Biol. (2004)
11
![Page 12: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/12.jpg)
Structural model of PC645 (Chroomonas)
12
![Page 13: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/13.jpg)
Assign the spectrum to structure
13
![Page 14: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/14.jpg)
Assign the spectrum to structure
DBV
PCB
MBV
14
![Page 15: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/15.jpg)
Coherence in cross-peak beats
!+ =1!2
!A!B + AB!"
!! =1!2
!A"B "AB""
15
![Page 16: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/16.jpg)
Electronic beats
!+ =1!2
!A!B + AB!"
!! =1!2
!A"B "AB""
A!, B!
!!=1 = ca!a + cb!b + cc!c
!!=1ab = cac!b
16
![Page 17: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/17.jpg)
Need information at the amplitude level
population/polarization grating
17
![Page 18: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/18.jpg)
τ T
Two-dimensional photon echo (2DPE)
18
![Page 19: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/19.jpg)
Interpreting 2DPE data
19
![Page 20: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/20.jpg)
Rephasing vs. non-rephasing signals
Yuan-Chung Cheng & Graham Fleming
20
![Page 21: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/21.jpg)
Coherence pathways in the signals
Yuan-Chung Cheng & Graham Fleming
21
![Page 22: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/22.jpg)
2DPE signals (real part) decomposed
22
![Page 23: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/23.jpg)
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.
23
![Page 24: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/24.jpg)
Electronic beats: rephasing spectra
24
![Page 25: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/25.jpg)
Electronic beats
25
![Page 26: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/26.jpg)
Electronic beats: rephasing spectra
26
![Page 27: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/27.jpg)
Coherence beats (PC645): non-rephasing
2.11 eV
2.185 eV
2.06 eV
2.11 eV
2.185 eV2.06 eV
~600 cm–1
27
![Page 28: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/28.jpg)
Coherence beats (PC645): non-rephasing
2.11 eV
2.185 eV
2.06 eV
2.11 eV
2.185 eV2.06 eV
2.11 eV
2.185 eV
2.06 eV
~600 cm–1
~380 cm–1
2.11 eV
28
![Page 29: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/29.jpg)
Coherently ‘wired’ energy migration
29
![Page 30: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/30.jpg)
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).
30
![Page 31: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/31.jpg)
Weak and strong coupling regimes
31
![Page 32: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/32.jpg)
Limits of the dynamics
Förster theory Redfield theory, etc
weak electronic coupling
strong electronic coupling
32
![Page 33: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/33.jpg)
PC645 trajectories: weak coupling to MBV
18.0
17.5
17.0
16.5
16.0
x103
1000080006000400020000
-0.4-0.3-0.2-0.10.0
1000080006000400020000
Ener
gy
Time (fs)
E!=1
E!=2
E!=3
!!=1 = ca!a + cb!b + cc!c
!!=1ab = cac!b
!!=1ab
33
![Page 34: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/34.jpg)
PC645 trajectories
18.0
17.5
17.0
16.5
16.0
x103
1000080006000400020000
-0.4-0.3-0.2-0.10.0
1000080006000400020000
Ener
gy
Time (fs)
!!=1ab
34
![Page 35: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/35.jpg)
What limits the exciton diffusion length?
ultrafast energyrelaxation/transfer
35
![Page 36: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/36.jpg)
Energy migration along a PPV chain
36
![Page 37: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/37.jpg)
Energy transfer in PPV chains
Jay Singh, Eric Bittner, David Beljonne, GDS (2009).
37
![Page 38: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/38.jpg)
Ultrafast anisotropy decay
38
![Page 39: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/39.jpg)
Photon echo spectroscopy
population/polarization grating
39
![Page 40: Department of Chemistry, University of Torontopbtz/doc/quebs09/slides/QuEBS09... · Department of Chemistry, University of Toronto 1. Alumni: Karyn Ang Dr. Vitalij Kovalevskij Dr.](https://reader033.fdocuments.net/reader033/viewer/2022042108/5e887ec80fdff101a67a0af0/html5/thumbnails/40.jpg)
Coherence-mediated energy transfer
293 K
Elisabetta Collini & GDS, Science 323, 369–373 (2009). J Phys Chem A 113, 4223–4241 (2009).
40