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)


initially-displacedwave packet



state-1’(ge)

state-1(eg)



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 …



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






+−















+−










for example, nl-WPI signal contribution with phase-signature

S+− =S1+−+S1'

+−exp iϕ BA −iϕ DC{ } is with






+−












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


initial trajectories in donor-excited state

state-1’ (ge)

state-1 (eg)


wave 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


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


(simulated-emission contribution to) pump-probe & pump-probe difference

signals from an oriented sample

1’

1


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?



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


ε ′1 = ε1 − 2ωδ 2

ΩC =ε1 −3δ 2ω ΩA =ε1 +δ 2ω

δ = 2.5J =0.2ω


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


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



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


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


(t −tA) / τ vib



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?

vibrational coherence transfer in lh-1 & prospects for vibrational control of

Documents

pumpprobe limit of nl

donorexcited statestate

wpi difference measurement

nlwpi signal contribution

nuclear wave packet

shorttime eetbiggs cinajcp

pulse sequence

van mourik van grondelle