vibrational coherence transfer in LH-1 & prospects for vibrational control of
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Transcript of vibrational coherence transfer in LH-1 & prospects for vibrational control of
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vibrational coherence transfer in LH-1 &vibrational coherence transfer in LH-1 &prospects for vibrational control of prospects for vibrational control of
electronic excitation transferelectronic excitation transfer
jason biggs &jason biggs & jeff cinajeff cinadepartment of chemistry & oregon center for opticsdepartment of chemistry & oregon center for optics
university of oregonuniversity of oregon
supported bysupported byus-nsf &us-nsf &acs-prfacs-prf
ultrafast absorption-difference at 5 Kmonshouwer, baltuska, van mourik
& van grondelle, j. phys. chem. a 1998
photosynthetic electronic energy transfer can be accompanied by vibrational coherence transfer
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LH1-RC structurecogdell et al. science 2003
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fluorescence up-conversionat room temperaturebradforth, jimenez, van mourik, van grondell & fleming, j. phys. chem. 1995
vibrational coherencetransfer and trapping …energy transfer complexescina & flemingj phys chem a 2004
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state-1(eg)
state-1’(ge)
state-1’(ge)
state-1(eg)
franck-condon-excitedwave packet
wave-packet trajectory in donor-excited stateaffects short-time EETbiggs & cinajcp submitted 2009
state-1’(ge)
state-1(eg)
franck-condon-excitedwave packet
initially-displacedwave packet
wave-packet trajectory in donor-excited stateaffects short-time EETbiggs & cinajcp submitted 2009
wave-packet trajectory in donor-excited stateaffects short-time EETbiggs & cinajcp submitted 2009
state-1’(ge)
state-1(eg)
franck-condon-excitedwave packet
initially-displacedwave packet
Peg(t)
1’
1
donor-state population
oriented model system
horizontally polarized pump without or with
priordisplacement to qb=
- d
vibrationally-perturbed nl-WPI (& pump-probe spectroscopy) on a collection of identical, randomly oriented dimers
H = 0 H0 0 + 1 H1 1 + ′1 H ′1 ′1 + 2 H2 2 + J ′1 1 + 1 ′1{ }
0 = gg 1 = eg
′1 = ge 2 = ee
both monomers unexcited —>
“acceptor” excited —> <— both monomers excited
<— “donor” excited
signal is the population of one-exciton manifold 2nd-order in sub-resonant “control” pulse and quadrilinear in the wpi-pulses
having a given optical phase-signature
P A B C D
I ⋅⋅⋅ I I ⋅⋅⋅⋅ I I
tP tA tB tC tD
ϕ BA ϕ DC
all pulsesnonzero duration,
independentlypolarized
pulsesequence:
in the pump-probe limit of nl-WPI difference measurement,pulse sequence simplifies …
P A B C D
I ⋅⋅⋅ I I ⋅⋅⋅⋅ I I
tP tA tB tC tD
ϕ BA ϕ DC
P A & B C & D
I ⋅⋅⋅ I ⋅⋅⋅⋅ I
tP tA =tB tC =tD
ϕ BA ϕ DC
in the pump-probe limit of nl-WPI difference measurement,pulse sequence simplifies …
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Sε+− = B( )ε CDAPP( )ε
+−+ B( )ε DCAPP( )ε
+−+ BPP( )ε CDA( )ε
+−
+ BPP( )ε DCA( )ε+−
+ CDBPP( )ε A( )ε+−
+ DCBPP( )ε A( )ε+−
+ CDB( )ε APP( )ε+−
+ DCB( )ε APP( )ε+−
+ C( )ε DBAPP( )ε+−
+ CPP( )ε DBA( )ε+−
+ CABPP( )ε D( )ε+−
+ CAB( )ε DPP( )ε+−
for example, nl-WPI signal contribution with phase-signature
S+− =S1+−+S1'
+−exp iϕ BA −iϕ DC{ } is with
Sε++ =Sε
+− =Sε−− =Sε
−+(tBA =tDC =0)
Θε =8Re C( )εDBAPP( )ε
+−+ CPP( )ε
DBA( )ε
+−⎡⎣
⎤⎦
+8Re B( )εCDAPP( )ε
+−+ BPP( )ε
CDA( )ε
+−⎡⎣
⎤⎦
+8Re B( )εDCAPP( )ε
+−+ BPP( )ε
DCA( )ε
+−⎡⎣
⎤⎦
pump-probe limit :
← GSB
← ESA
← SE
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Sε+− = B( )ε CDAPP( )ε
+−+ B( )ε DCAPP( )ε
+−+ BPP( )ε CDA( )ε
+−
+ BPP( )ε DCA( )ε+−
+ CDBPP( )ε A( )ε+−
+ DCBPP( )ε A( )ε+−
+ CDB( )ε APP( )ε+−
+ DCB( )ε APP( )ε+−
+ C( )ε DBAPP( )ε+−
+ CPP( )ε DBA( )ε+−
+ CABPP( )ε D( )ε+−
+ CAB( )ε DPP( )ε+−
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Sε+− = B( )ε CDAPP( )ε
+−+ B( )ε DCAPP( )ε
+−+ BPP( )ε CDA( )ε
+−
+ BPP( )ε DCA( )ε+−
+ CDBPP( )ε A( )ε+−
+ DCBPP( )ε A( )ε+−
+ CDB( )ε APP( )ε+−
+ DCB( )ε APP( )ε+−
+ C( )ε DBAPP( )ε+−
+ CPP( )ε DBA( )ε+−
+ CABPP( )ε D( )ε+−
+ CAB( )ε DPP( )ε+−
for example, nl-WPI signal contribution with phase-signature
S+− =S1+−+S1'
+−exp iϕ BA −iϕ DC{ } is with
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Sε+− = B( )ε CDAPP( )ε
+−+ B( )ε DCAPP( )ε
+−+ BPP( )ε CDA( )ε
+−
+ BPP( )ε DCA( )ε+−
+ CDBPP( )ε A( )ε+−
+ DCBPP( )ε A( )ε+−
+ CDB( )ε APP( )ε+−
+ DCB( )ε APP( )ε+−
+ C( )ε DBAPP( )ε+−
+ CPP( )ε DBA( )ε+−
+ CABPP( )ε D( )ε+−
+ CAB( )ε DPP( )ε+−
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DCA( )ε =e−iϕ A + iϕ DC [eA ′eC ′eD d(12)c(21)a(10){ } ε
+eA ′eCeD d( ′1 2)c(21)a(10){ } ε + eAeC ′eD d(12)c(2 ′1 )a(10){ } ε
+eAeCeD d( ′1 2)c(2 ′1 )a(10){ } ε + ′eA ′eC ′eD d(12)c(21)a( ′1 0){ } ε
+ ′eA ′eCeD d( ′1 2)c(21)a( ′1 0){ } ε + ′eAeC ′eD d(12)c(2 ′1 )a( ′1 0){ } ε
+ ′eAeCeD d( ′1 2)c(2 ′1 )a( ′1 0){ } ε ]+e−iϕ A −iϕ DC [eAeCeD d(10)c(01)a(10){ } ε
+eAeC ′eD d( ′1 0)c(01)a(10){ } ε + eA ′eCeD d(10)c(0 ′1 )a(10){ } ε
+eA ′eC ′eD d( ′1 0)c(0 ′1 )a(10){ } ε + ′eAeCeD d(10)c(01)a( ′1 0){ } ε
+ ′eAeC ′eD d( ′1 0)c(01)a( ′1 0){ } ε + ′eA ′eCeD d(10)c(0 ′1 )a( ′1 0){ } ε
+ ′eA ′eC ′eD d( ′1 0)c(0 ′1 )a( ′1 0){ } ε ] .
the corresponding nuclear wave packet is a linear superposition of the form
electronic state-space pathways contributing to
DCA( )ε
initial trajectories in donor-excited state
state-1’ (ge)
state-1 (eg)
franck-condon-excited
wave packet
initially-displacedwave packet
initial trajectories in donor-excited state
state-1’ (ge)
state-1 (eg)
franck-condon-excited
wave packet
initially-displacedwave packet
wave packetgenerated byISRS & short-
pulse electronicabsorption
ISRS generates nuclear motion withmaximum displacement less than d
donor-excited state population
donor-state population of oriented model system after interaction with vertically polarized ISRS & horizontally polarized pump pulses
1’
1
franck-condon-excitedwave packet
ISRS-generated wave packet q
b(t
A) =−0.34d=1.07Δqrms
ΩC =ε −3δ 2ω ΩA =ε +δ 2ω
δ = 2.5J =0.2ω
pump-probe & pump-probe difference signals
from isotropic sample
without & with stimulated-Raman excitation
P-pulseISRS
polarization
pump (A) &probe (C)
polarization
1⊥1'
ΩP =ε −1.91ω
σ P =0.14τ vib
σC =0.15τ vib σ A =0.1τ vib
ΩC =ε −3δ 2ω ΩA =ε +δ 2ω
δ = 2.5J =0.2ω
P-pulseISRS
polarization
pump (A) &probe (C)
polarization
ΩP =ε −1.91ω
σ P =0.14τ vib
σC =0.15τ vib σ A =0.1τ vib
(simulated-emission contribution to) pump-probe & pump-probe difference
signals from an oriented sample
1’
1
pump-probe & pump-probe difference signals
from isotropic, inhomogeneously broadened sample
site energies chosen from independent Gaussian distributions of FWHM ω
pulse parameters same as before, except σ A =0.25τ vib and
σC =0.5τ vib
accelerated EET in the downhill case?
initially-displacedwave packet
franck-condon-excited
wave packet
donor-excited state population in downhill EET
donor-state population of oriented downhill system after interaction with vertically polarized ISRS & horizontally polarized pump pulses
1’
1
ISRS-generated wave packet
franck-condon-excitedwave packet
ε ′1 = ε1 − 2ωδ 2
ΩC =ε1 −3δ 2ω ΩA =ε1 +δ 2ω
δ = 2.5J =0.2ω
pump-probe & pump-probe difference signals
from isotropic sample of downhill EET complex
P-pulseISRS
polarization
pump (A) &probe (C)
polarization
1⊥1'
ΩP =ε ′1 −1.91ω
σ P =0.14τ vib
σC =0.15τ vib σ A =0.1τ vib
VHH
HH
pump-probe difference signal
pum
p-pr
obe
sign
al
VHH
HH
contributions to signals fromdownhill EET complex:
stimulated-emission
excited-state absorption
ground-state bleach
ΩC =ε ′1 −3δ 2ω ΩA =ε1 +δ 2ω
δ = 2.5J =0.2ω
ISRS (P) &probe (C)
polarization
pump (A)polarization
1⊥1'
ΩP =ε ′1 −1.91ω
σ P =0.14τ vib
σC =0.15τ vib σ A =0.1τ vib
pump-probe & pump-probe difference signals
from isotropic sample of downhill EET complex
V-polarized & red-shifted probe
VHV
HV
dithia-anthracenophane (DTA)
anthracene monomer fluorescence
lambert et al. JCP 1984
DTA fluorescence anisotropy
yamazaki et al.j phys chem A 2002
ω12 = 385 cm-1
δ12 = 0.557
J = 22.9 cm-1
ω = 1400 cm-1
δ = 1.05
pulse power spectra & schematic absorption spectrapulse power spectra & schematic absorption spectra
P-pulse (ISRS)P-pulse (ISRS)
anthraceneanthracene anthracene-12anthracene-12
A-pulse (pump)C-pulse (probe)C-pulse (probe)
(t - tA)/τ12
donor-state population
σ P =0.225τ12 =20 fs
ΩP =ε −1.53ω12
qb (tA ) =−0.54d12
=−0.0Δq12
σ A =0.10 τ12 =9 fs
ΩA =ε +δ122ω12
=ε + 0.31ω12
withISRS
withoutISRS
DTA-12 donor-state population dynamics
1 ⊥ 1'
polarized pump-probe & pump-probe difference signals from DTA-12
σC =0.5τ12
=43 fs
pump-probe
pump-probe difference
VHH
HH
anisotropy
stimulated-emission only
σ A =0.25τ12
other parameters the same, except
100-cm-1 site-energy broadening
(tC −tA ) / τ12
(tC −tA ) / τ12
(2A ) ′1 (2A)1 =-0.0351
P1(t) ≅12+12
(νSνA)1 ψ 1νS ,νA
∑ 2cos 2tJ (νA) ′1 (νA)1⎡⎣ ⎤⎦
qb/d
when , the survival probability reduces to J <<ω
idiosyncracies of (antisymmetric-mode) Franck-Condon overlaps may
offer a prospect for exerting vibrational control over EET, even in the
weak electronic-vibrational coupling case . (δ <<ω)
in DTA-12, for example,
ψ 1 = eipb d (0S2A )0
qa/d
donor-state population
(t −tA) / τ vib
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next steps …next steps …
vibrational control of EET in (biological?) multi-chromophore complexes
optimize duration, center frequency, and chirp-rate of P-pulsefor large-amplitude acceptor-mode displacement
calculate & interpret full nl-WPI difference signals,with all polarization combinations
include vibrational relaxation and dephasing via Redfield theory
calculate & interpret nl-WPI difference signals from Jahn-Telleractive (or other) systems with conical intersections following ISRS-excitation
of coherent pseudo-rotation; prepare & observedynamical Slonczewski resonances?
vibrational control of EET in (biological?) multi-chromophore complexes
optimize duration, center frequency, and chirp-rate of P-pulsefor large-amplitude acceptor-mode displacement
calculate & interpret full nl-WPI difference signals,with all polarization combinations
include vibrational relaxation and dephasing via Redfield theory
calculate & interpret nl-WPI difference signals from Jahn-Telleractive (or other) systems with conical intersections following ISRS-excitation
of coherent pseudo-rotation; prepare & observedynamical Slonczewski resonances?