Vibrational polariton chemistry · 2020. 7. 20. · Theory: QOptics + QChem J. Collett and C. W....
Transcript of Vibrational polariton chemistry · 2020. 7. 20. · Theory: QOptics + QChem J. Collett and C. W....
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Vibrational polariton chemistry
JOEL YUEN-ZHOUUniversity of California San DiegoDepartment of Chemistry and Biochemistry
Molecular polaritonics, Madrid, July 2019
Follow us @ucsd_yuen
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Research on theoretical
molecular photonics
Condensed
matter
Quantum
optics
Physical/theoretical
chemistry
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The group and the campus
December 2018 UC San Diego
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The group
Group photo, UCSD December 2018
Jorge and Matt,
COMICON July 2018
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Introduction
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One molecule in a cavity: Jaynes-Cummings
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One molecule in a cavity: Jaynes-Cummings
Juan Bernardo
Pérez-SánchezPOSTER: Polariton-assisted photon
downconversion
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Many molecules in a cavity: Tavis-Cummings
Rabi splitting Ω = 2 𝑁ℏ𝑔𝑠 where 𝑁 = 106 − 1010
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Many molecules in a cavity: Tavis-Cummings
𝑊 𝐶𝑂 6
𝜔10 = 1983 𝑐𝑚−1
B. Xiang, R. F. Ribeiro, A. D. Dunkelberger, J. C. Owrutsky,
B. S. Simpkins, J. Yuen-Zhou, and W. Xiong,
PNAS 115, 19 (2018).
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Many molecules in a cavity: Tavis-Cummings
HMPP
𝜔10 = 3.6 𝑒𝑉
D.P. Kizhmuri, R. Desmukh, L. Martínez, J. Yuen-Zhou, E.
Hohenstein, G. John, V. Menon, in preparation.
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The various regimes of light-matter coupling
Kockum, Anton Frisk, et al. "Ultrastrong coupling between light
and matter." Nature Reviews Physics 1.1 (2019): 19.
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MOTIVATION: Why
molecular polaritons?
Polariton devices
D. Ballarini, et al., Nature Commun. 4, 1778 (2013)
Polariton condensates
E.R. Bittner and C. Silva, J. Chem. Phys. 136.3 (2012): 034510.K. S. Daskalakis, et. al., Nat. Mater. 13, 271-278 (2014)
Polariton chemistryV. M. Agranovich, et al, PRB 2003, 67, 085311.T.W. Ebbesen, Acc. Chem. Res. 49(11):2403-12;D.M. Coles, Nat. Mater. 13.7 (2014): 712;J. Flick, et al, PNAS 114.12 (2017): 3026-3034;J. Galego, et al, PRX 5.4 (2015) 041022; F. Herrera and F. Spano, PRL 116 23 (2016).M. Kowalewski, K. Bennett, and S. Mukamel, J. Phys. Chem. Lett. 7 11 (2016) 2050-2054.
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Chem. Sci., 9, 6325-6339 (2018)
See also reviews by Ebbesen, Feist, Shegai, Narang
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Outline of talk
Nonlinearities
Remote control
Vibrational
polaritons
Ground-state
reactivity
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Outline of talk
Nonlinearities
Remote control
Vibrational
polaritons
Ground-state
reactivity
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Polariton chemistry in the dark?
ℏ𝜔𝑚 = 860 𝑐𝑚−1
Ω𝑉𝑅 = 90 𝑐𝑚−1
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Polariton chemistry in the dark? Our thoughts a year agoIn
sid
e o
f th
e c
avity
Ou
tsid
e o
f th
e c
avity
R
R*
P
P*
R
darkLP
UP
P
P*
(Koreatown - LA, February 2018)
[𝑑𝑎𝑟𝑘]
[𝐿𝑃]= 1010 at 298 K ⇒ 𝑅∗ ≈ 𝑑𝑎𝑟𝑘 .
Dark states behave like bare molecular excitations.
Reactivity in cavity should be equal to reactivity out
of the cavity.
𝑑 𝑃∗
𝑑𝑡= 𝑘[𝑅∗]
𝑑 𝑃∗
𝑑𝑡= 𝑘[𝑑𝑎𝑟𝑘]
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Polariton chemistry in the dark? Our present thoughts
We have theoretically
developed the first
model where vibrational
strong coupling (VSC)
can lead to electron
transfer catalysis.
J. Campos-González-Angulo, R.F. Ribeiro, J. Yuen-Zhou, arXiV:1902.10264.
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Polariton chemistry in the dark? Our present thoughts
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Background: Marcus theory
As the reaction becomes more exergonic (larger
− Δ𝐺), the reaction can become slower!
R R R
P
P
P
En
erg
y
Classical outer sphere reaction coordinate 𝑞𝑠
Normal regime Inverted regime
Rudolph Marcus
(1956)
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Gerhard Closs
(1984)
Background: Marcus theory
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P
Marcus inverted regime
R
Background: Marcus theory - a caveat due to Jortner
Joshua Jortner
(1976)
En
erg
y
Classical outer sphere reaction coordinate 𝑞𝑠
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Joshua Jortner
(1976)
A slow rate in the Marcus inverted
regime can be accelerated by creating a
high-frequency 𝜔𝑃 vibrational
excitation in the acceptor.
ℏ𝜔𝑃En
erg
y
Classical outer sphere reaction coordinate 𝑞𝑠
R
P1
P0
Background: Marcus theory - a caveat due to Jortner
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Catalysis of Marcus-Jortner ET with an IR cavity
En
erg
y
P0
R
ℏ𝜔𝑃
{D}
LP
UP
𝑞𝑠J. Campos-González-Angulo, R.F. Ribeiro, J. Yuen-Zhou, arXiV:1902.10264.
Let cavity couple to the high-frequency modes of molecules undergoing ET. Place 𝑀 =1010 reactants in cavity. As rxn proceeds from R to P, coupling to light becomes stronger!
P1
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Anomalous kinetics a.k.a. leadership
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Catalysis of Marcus-Jortner ET with an IR cavity
En
erg
y
P0
R
ℏ𝜔𝑃
{D}
LP
UP
𝑞𝑠J. Campos-González-Angulo, R.F. Ribeiro, J. Yuen-Zhou, arXiV:1902.10264.
Place 𝑀 = 1010 reactants that undergo ET inside of a cavity. Let cavity couple to the
high-frequency modes of P. As rxn proceeds from R to P, coupling to light becomes
stronger!
P1
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Catalysis of Marcus-Jortner ET with an IR cavity
J. Campos-González-Angulo, R.F. Ribeiro, J. Yuen-Zhou, arXiV:1902.10264.
ΩN=M
𝑘R→LP 𝑁 > 𝑘R→{D}⇒ 𝑘𝑖𝑛 > 𝑘𝑜𝑢𝑡
𝑁 = # P molecules formed.
𝑁 ≤ 𝑀 = 1010 total # molecules.
If we want:
We need:
Activation energy reduction due to LP can outcompete large activation entropy of {D}!!!
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Catalysis of Marcus-Jortner ET with an IR cavity
J. Campos-González-Angulo, R.F. Ribeiro, J. Yuen-Zhou, arXiV:1902.10264.
ΩN=M
Activation energy reduction due to LP can
outcompete large activation entropy of
{D}!!!
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Catalysis of Marcus-Jortner ET with an IR cavity
J. Campos-González-Angulo, R.F. Ribeiro, J. Yuen-Zhou, arXiV:1902.10264.
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The reaction that we are interested is in principle 𝑁 + 1 body,
Catalysis of Marcus-Jortner ET with an IR cavity
but can be reduced to an effective 3-body process,
See also: A. Strashko, A. & J. Keeling, (2016), Physical Review A, 94(2), 023843.
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leading to a Marcus-Jortner-type expression of the form,
Catalysis of Marcus-Jortner ET with an IR cavity
Jorge Campos
J. Campos-González-Angulo, R.F. Ribeiro, J. Yuen-Zhou, arXiV:1902.10264.
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Summary #1
❖ VSC can in fact lead to catalysis of thermally-activated ground state reactions.
❖ The elucidated mechanism operates for reactions with large activation energy barriers.
❖ It does not lead to (direct) suppression of reactions.
❖ Is quantum mechanics important for VSC rxns?
S. Kena-Cohen and J. Yuen-Zhou, ACS Cent. Sci., First reactions, 2019.
J. Campos-González-Angulo, R.F. Ribeiro, J. Yuen-Zhou, arXiV:1902.10264.
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SIMILAR PROBLEM: Harvesting of triplets: the idea
Electrical injection of excitons statistically generates 3 triplets
per singlet. Triplets don’t give rise to PL.
L.A. Martínez-Martínez, E. Eizner, S. Kena-Cohen, J. Yuen-Zhou, J. Chem. Phys., in press
E. Eizner, L.A. Martínez-Martínez, J. Yuen-Zhou, S. Kena-Cohen, arXiV:1903.09251
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SIMILAR PROBLEM: Harvesting of triplets: gets worse with larger N
As the number of
molecules 𝑁 in the cavity
becomes larger, the
fluorescence efficiency
decreases. The maximum
rate is bounded at
𝑘𝑇→𝐿𝑃 ≤𝑉𝑆𝑇
2
2ℏ𝑁
𝜋
𝜆𝑇,𝐿𝑃𝑘𝐵𝑇 SS
S
SS
S
SS
S
TT
T
TT
T
TT
T
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Harvesting of triplets: the experiment
Goushi, K., Yoshida, K., Sato, K. & Adachi, C.,
Nat. Photonics 6, 253–258 (2012)
E. Eizner, L.A. Martínez-Martínez, J. Yuen-Zhou, S.
Kena-Cohen, arXiV:1903.09251
No changes in triplet lifetime was
observed in experiment with
3DPA3CN when put in a
microcavity!
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Outline of talk
Nonlinearities
Remote control
Vibrational
polaritons
Ground-state
reactivity
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Outline of talk
Nonlinearities
Remote control
Vibrational
polaritons
Ground-state
reactivity
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Acknowledgements
Adam Dunkelberger Jeff OwrutskyBo XiangWei Xiong
Raphael
Ribeiro
Naval Research LaboratoryUC San Diego
Blake Simpkins
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𝑊 𝐶𝑂 6
𝜔10 = 1983 𝑐𝑚−1
Dunkelberger et al. Nat. Comm. 7, 13504, 2016
The experiment #1
Linear absorption Transient absorption
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The experiment #2
Nonlinear spectroscopy provides a variety of spectral projections of the many-body response.
Wei Xiong Bo Xiang
B. Xiang, R. F. Ribeiro, A. D. Dunkelberger, J. C. Owrutsky, B. S. Simpkins, J.
Yuen-Zhou, and W. Xiong, PNAS 115, 19 (2018).
R.F. Ribeiro, R. F. Ribeiro, A. D. Dunkelberger, J. C. Owrutsky, B. S. Simpkins,
W. Xiong, J. Yuen-Zhou, J. Phys. Chem. Lett. 9, 13 (2018).
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The experiment #2
UP
LP
LPUP
bare
Blake
Simpkins
What are those derivative lineshapes?
B. Xiang, R. F. Ribeiro, A.
D. Dunkelberger, J. C.
Owrutsky, B. S. Simpkins, J.
Yuen-Zhou, and W. Xiong,
PNAS 115, 19 (2018).
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Theory: QOptics + QChem
J. Collett and C. W. Gardiner, PRA 30, 1386 (1984)
C. W. Gardiner and M. J. Collett, PRA 31, 3761 (1985)
Input-output theory
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Theory: QOptics + QChem
J. Collett and C. W. Gardiner, PRA 30, 1386 (1984)
C. W. Gardiner and M. J. Collett, PRA 31, 3761 (1985)
Input-output theory Anharmonic vibrations in condensed phase
M. Khalil, N. Demirdöven, and A. Tokmakoff, J. Phys.
Chem. A, 107.27 (2003): 5258-5279.
B. Xiang, R. F. Ribeiro, A. D. Dunkelberger, J. C. Owrutsky, B. S. Simpkins, J. Yuen-Zhou, and W. Xiong, PNAS 115, 19 (2018).
R.F. Ribeiro, R. F. Ribeiro, A. D. Dunkelberger, J. C. Owrutsky, B. S. Simpkins, W. Xiong, J. Yuen-Zhou, J. Phys. Chem. Lett. 9, 13 (2018).
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Refresher on nonlinear optics
Harmonic oscillator
Anharmonic oscillator
𝜔0
𝜔0
𝜔0 − Δ
𝜔0
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Refresher on nonlinear optics
Harmonic oscillator
Anharmonic oscillator
𝜔0
𝜔0
𝜔0 − Δ
𝜔0
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Refresher on nonlinear optics
Harmonic oscillator
Anharmonic oscillator
𝜔0
𝜔0
𝜔0 − Δ
𝜔0
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Refresher on nonlinear optics
Harmonic oscillator
Anharmonic oscillator
𝜔0
𝜔0
𝜔0 − Δ
𝜔0
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Refresher on nonlinear optics
Harmonic oscillator
Anharmonic oscillator
𝜔0
𝜔0
𝜔0 − Δ
𝜔0
𝜔0 − Δ
𝜔0
Harmonic systems exhibit
no nonlinear response!
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Theory: QOptics + QChem
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𝜸𝑭←𝑰 =𝟐𝝅
ℏ
𝒇
𝒊
𝒑𝒊 𝒇 𝑽 𝒊 𝟐𝝆(ℏ𝝎𝒇,𝒊)
Some timescales to keep in mind
~10-100 ps
~50 fs
1 𝜇s~
In condensed phases, vibrational
couplings 𝑉 lead to relaxation
mechanisms.
Ribeiro RF, Martínez-Martínez LA, Du M, Campos-Gonzalez-Angulo J, Yuen-Zhou J. Polariton Chemistry:
controlling molecular dynamics with optical cavities, Chem. Sci., 9, 6325-6339 (2018).
~50-100 fs
~50 fs
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|1𝑣⟩|𝑝ℎ⟩
|𝑔⟩
|2𝑣⟩
|1𝑣⟩
(a) Ultrafast switching of polaritons: saturation effects (t2>20 ps)
|𝑈𝑃⟩
|𝐿𝑃⟩
With pump
Without pump
Δ𝑇 = With pump -
Without pump
B. Xiang, R. F. Ribeiro, A. D. Dunkelberger, J. C. Owrutsky, B. S. Simpkins, J. Yuen-Zhou, and W. Xiong, PNAS 115, 19 (2018).
R.F. Ribeiro, R. F. Ribeiro, A. D. Dunkelberger, J. C. Owrutsky, B. S. Simpkins, W. Xiong, J. Yuen-Zhou, J. Phys. Chem. Lett. 9, 13 (2018).
With pump
Without pump
Δ𝑇 = With pump
- Without pump
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|1𝑣𝐵⟩|𝑝ℎ⟩
|𝑔⟩
|2𝑣⟩
{|1𝑣𝐷⟩}
(a) Ultrafast switching of polaritons: saturation effects (t2>20 ps)
|𝑈𝑃⟩
|𝐿𝑃⟩
With pump
Without pump
Δ𝑇 = With pump -
Without pump
B. Xiang, R. F. Ribeiro, A. D. Dunkelberger, J. C. Owrutsky, B. S. Simpkins, J. Yuen-Zhou, and W. Xiong, PNAS 115, 19 (2018).
R.F. Ribeiro, R. F. Ribeiro, A. D. Dunkelberger, J. C. Owrutsky, B. S. Simpkins, W. Xiong, J. Yuen-Zhou, J. Phys. Chem. Lett. 9, 13 (2018).
With pump
Without pump
Δ𝑇 = With pump
- Without pump
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40mM W(CO)6 in
n-hexane solution
B. Xiang, R. F. Ribeiro, A. D. Dunkelberger, J. C. Owrutsky, B. S. Simpkins, J. Yuen-Zhou, and W. Xiong, PNAS 115, 19 (2018).
R.F. Ribeiro, R. F. Ribeiro, A. D. Dunkelberger, J. C. Owrutsky, B. S. Simpkins, W. Xiong, J. Yuen-Zhou, J. Phys. Chem. Lett. 9, 13 (2018).
(a) Ultrafast switching of polaritons: saturation effects (t2>20 ps)
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Length L
Prof. Wei Xiong and his student Bo Xiang changed the cavity length from L to 2L while keeping concentration (Rabi splitting) fixed. They saw:a. Same nonlinear signal.b. Weaker nonlinear signal.c. Stronger nonlinear signal.
(a) “Clicker” question
?
L
2L
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Length L
Length 2L
Anharmonicity is local, but polariton is spread
out across the cavity!
Weaker nonlinearities for larger samples of same concentration!
B. Xiang, R. F. Ribeiro, Y. Li, A. D. Dunkelberger, B. B. Simpkins, J. Yuen-Zhou, W. Xiong, arXiV: 1901.05526
(a) Ultrafast switching of polaritons: saturation effects (t2>20 ps)
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B. Xiang, R. F. Ribeiro, Y. Li, A. D. Dunkelberger, B. B. Simpkins, J. Yuen-Zhou, W. Xiong, arXiV: 1901.05526
(b) Ultrafast switching of polaritons: coherent effects (T<20 ps)
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B. Xiang, R. F. Ribeiro, Y. Li, A. D. Dunkelberger, B. B. Simpkins, J. Yuen-Zhou, W. Xiong, arXiV: 1901.05526
(b) Ultrafast switching of polaritons: coherent effects (T<20 ps)
|1𝑣⟩|𝑝ℎ⟩
|𝐿𝑃, 𝑈𝑃⟩
|𝐿𝑃⟩
|1𝑖 , 1𝑗⟩
|𝑈𝑃⟩
pro
be
Nonlinear dephasing
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Summary #2
❖ Obtained and explained first vibrational polariton 2D spectra.
❖ Larger polariton samples have weaker nonlinearities.
❖ Coherent nonlinear optical “polariton bleach” effect (nonlinear dephasing) at short times.
B. Xiang, R. F. Ribeiro, A. D. Dunkelberger, J. C. Owrutsky, B. S. Simpkins, J. Yuen-Zhou, and W. Xiong, PNAS 115, 19 (2018).
R.F. Ribeiro, R. F. Ribeiro, A. D. Dunkelberger, J. C. Owrutsky, B. S. Simpkins, W. Xiong, J. Yuen-Zhou, J. Phys. Chem. Lett. 9, 13 (2018).
B. Xiang, R. F. Ribeiro, Y. Li, A. D. Dunkelberger, B. B. Simpkins, J. Yuen-Zhou, W. Xiong, arXiV: 1901.05526
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Outline of talk
Nonlinearities
Remote control
Vibrational
polaritons
Ground-state
reactivity
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Outline of talk
Nonlinearities
Remote control
Vibrational
polaritons
Ground-state
reactivity
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Forster Resonance Energy Transfer (FRET)
Energy transfer across ~10 nm.
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Forster (1948)
g
e
Monomer
g
e
Monomer
Excitation energy transfer: two cases
Davydov (1948)/Redfield (1965)
V<<coupling to phononsV>>coupling to phonons
A. Tokmakoff (UChicago, online notes)
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Forster (1948)
Excitation energy transfer: two cases
Davydov (1948)/Redfield (1965)
V<<coupling to phononsV>>coupling to phonons
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Polariton assisted remote energy transfer (PARET)
M. Du, L.A. Martinez-Martinez, R.F. Ribeiro,
V.M. Menon, J. Yuen-Zhou, Chem. Sci. 9,
6659-6669 (2018).
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Polariton assisted remote energy transfer (PARET)
M. Du, L.A. Martinez-Martinez, R.F. Ribeiro,
V.M. Menon, J. Yuen-Zhou, Chem. Sci. 9,
6659-6669 (2018).
Zhong et al., Angew.
Chem., Int. Ed., 2017, 56, 9034–9038.
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Is remote control of chemistry possible?
Matthew Du Raphael Ribeiro
Acknowledgements
![Page 67: Vibrational polariton chemistry · 2020. 7. 20. · Theory: QOptics + QChem J. Collett and C. W. Gardiner, PRA 30, 1386 (1984) C. W. Gardiner and M. J. Collett, PRA 31, 3761 (1985)](https://reader036.fdocuments.us/reader036/viewer/2022081621/6121b0459e68216f4242e413/html5/thumbnails/67.jpg)
pump delay probe
From PARET to remote control of chemistry
cis-HONO
Isomerization
trans-HONO
ONOFF
PUMP
REACT!
𝝎𝑶𝑵
𝝎𝑶𝑭𝑭
Left cavity
Right cavity
M. Du, R. F. Ribeiro, J. Yuen-Zhou, Chem. 5, 1167-1181 (2019)
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From PARET to remote control of chemistry
M. Du, R. F. Ribeiro, J. Yuen-Zhou, Chem. 5, 1167-1181 (2019)
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IR-induced, vibrationally-selective chemistry:
cis→trans isomerization of HONO
|0⟩
|𝑐𝑖𝑠, 1𝑣𝑂𝐻⟩cis trans
cis trans
R. T. Hall and G. C. Pimentel, JCP, 1963, 38, 1889.
R. Schanz, V. Botan, and P. Hamm, JCP, 2005, 122, 044509.
IVR
|𝜏⟩
~10 𝑝𝑠
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|1𝑣⟩|𝑝ℎ⟩
|𝑔⟩
|2𝑣⟩
|1𝑣⟩
Ultrafast switching of polaritons
|𝑈𝑃⟩
|𝐿𝑃⟩
With pump
Without pump
Δ𝑇 = With pump
- Without pump
B. Xiang, R. F. Ribeiro, A. D. Dunkelberger, J. C. Owrutsky, B. S. Simpkins, J. Yuen-Zhou, and W. Xiong, PNAS 115, 19 (2018).
R.F. Ribeiro, R. F. Ribeiro, A. D. Dunkelberger, J. C. Owrutsky, B. S. Simpkins, W. Xiong, J. Yuen-Zhou, J. Phys. Chem. Lett. 9, 13 (2018).
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Ultrafast remote-control chemistry
dark |𝑅, 1𝑣⟩ |𝑅, 1𝑣⟩|1𝑐←⟩
|𝑔⟩
dark |𝑐𝑖𝑠, 1𝑣𝑂𝐻 ⟩
|𝜏⟩
|1𝑐→⟩|𝑐𝑖𝑠, 1𝑣𝑂𝐻 ⟩
|𝑔⟩
Left cavity Right cavity
𝑐𝑖𝑠𝑐𝑅𝑐
|𝑔⟩
M. Du, R. F. Ribeiro, J. Yuen-Zhou, Chem. 5, 1167-1181 (2019)
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Ultrafast remote-control chemistry
Slow |𝜏⟩
|𝑔⟩
ΓOH = 5 𝑐𝑚−1
Γ𝜏 = 40 𝑐𝑚−1
M. Du, R. F. Ribeiro, J. Yuen-Zhou, Chem. 5, 1167-1181 (2019)
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Ultrafast remote-control chemistry
dark |𝑅, 1𝑣⟩ |𝑅, 1𝑣⟩|1𝑐←⟩
|𝑔⟩
dark |𝑐𝑖𝑠, 1𝑣𝑂𝐻 ⟩
|𝜏⟩
|1𝑐→⟩|𝑐𝑖𝑠, 1𝑣𝑂𝐻 ⟩
|𝑔⟩
𝑐𝑖𝑠𝑐𝑅𝑐
|𝑔⟩
pumpdelay
M. Du, R. F. Ribeiro, J. Yuen-Zhou, Chem. 5, 1167-1181 (2019)
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Ultrafast remote-control chemistry
dark |𝑅, 1𝑣⟩ |𝑅, 1𝑣⟩|1𝑐←⟩
|𝑔⟩
dark |𝑐𝑖𝑠, 1𝑣𝑂𝐻 ⟩
|𝜏⟩
|1𝑐→⟩|𝑐𝑖𝑠, 1𝑣𝑂𝐻 ⟩
|𝑔⟩|𝑔⟩
M. Du, R. F. Ribeiro, J. Yuen-Zhou, Chem. 5, 1167-1181 (2019)
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Slow |𝜏⟩
|𝑔⟩
|𝜏⟩
Ultrafast remote-control chemistry
Fast
No pump
After pump
|𝑔⟩
M. Du, R. F. Ribeiro, J. Yuen-Zhou, Chem. 5, 1167-1181 (2019)
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Pump tunes polariton energies on ultrafast timescale
Relax to
dark
remote
states
pump delay
cis-HONOremote
Linear absorption of pump
Bare vOH
energy
Bare
remote
energy
M. Du, R. F. Ribeiro, J. Yuen-Zhou, Chem. 5, 1167-1181 (2019)
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Pump tunes polariton energies on ultrafast timescale
pump delay probe
cis-HONO
Nonlinear absorption of probe
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Pump turns ON reaction on ultrafast timescale
pump delay probe
cis-HONO
𝜂 𝜔 = 𝐴𝑏𝑠𝑝𝑜𝑙𝑎𝑟𝑖𝑡𝑜𝑛 𝜔 × 𝑄𝑌 𝜔
= 𝐴𝑏𝑠𝑝𝑜𝑙𝑎𝑟𝑖𝑡𝑜𝑛 𝜔 × [𝑂𝑣𝑒𝑟𝑙𝑎𝑝 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝜔 𝑎𝑛𝑑 𝜔𝜏]
Nonlinear absorption of probe
ON
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Cavity-cavity coupling 𝒈𝒄 increases REACTION ENHANCEMENT of pump
pump delay probe
cis-HONO
M. Du, R. F. Ribeiro, J. Yuen-Zhou, Chem. 5, 1167-1181 (2019)
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Cavity-cavity coupling 𝒈𝒄 increases REACTION ENHANCEMENT of pump
pump delay probe
cis-HONO
M. Du, R. F. Ribeiro, J. Yuen-Zhou, Chem. 5, 1167-1181 (2019)
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Summary #3
❖ Nonlinear ultrafast switching of polaritons should allow for remote
control of a chemical reaction.
❖ Large tunability of efficiencies is expected for an IR-photoinduced
isomerization.
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Outline of talk
Nonlinearities
Remote control
Vibrational
polaritons
Ground-state
reactivity
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Other works: Photophysics
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Other works: Photophysics
2 3 4 5 6- 2.0
- 1.5
- 1.0
- 0.5
0.0
0.5
1.0
ΩλS
Δ λS
Fluorescence Yield (%)
4
8
12
16
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Other works: Ultrastrong coupling, Drexhage problem revisited
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Other works: How about DIRECTIONALITY of energy transfer?
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Other works: Topological effects in Born-Oppenheimer dynamics
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An outlook
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1920s 1960s 2012-
Einstein-Bohr
debatesCavity QED
Polariton
chemistry
Is cavity QED ready for chemistry?
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Chem. Sci., 9, 6325-6339 (2018)
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AcknowledgementsNSF CAREER Award #1654732
DOE Early Career Award DE-
SC0019188
AFOSR FA9550-18-1-0289
DARPA D19AC00011
UC/MEXUS-CONACYT
UC San Diego startup funds
Follow us in Twitter @ucsd_yuen