watching photo-induced structural dynamics with …pfwatching photo-induced structural dynamics with...
TRANSCRIPT
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Watching photoWatching photo--induced structural induced structural dynamics with timedynamics with time--resolved Xresolved X--ray ray
crystallography crystallography
Photon Factory, Photon Factory, KEKKEK
ERATO, JSTERATO, JST
ShinShin--ichi Adachiichi Adachi
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OutlineOutline
Why photoWhy photo--induced structural dynamics?induced structural dynamics?PhotoPhoto--stationary statestationary state
Photolysis of FePhotolysis of Fe--CO bond in hemoglobinCO bond in hemoglobin--CO CO
TimeTime--resolved measurementresolved measurementPhotoPhoto--induced phase transition in organic induced phase transition in organic charge transfer complex (TTFcharge transfer complex (TTF--CA, EDOCA, EDO--TTF)TTF)
Summary and future viewSummary and future view
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What crystallography can doWhat crystallography can do
Electron density distribution ofYBa
3D structure of Photosynthetic Cu O Oxygen Evolving Center2 3 7
(after Dr. Fujio Izumi’s HP)(45945 atoms)
(Ferreira et al. (2004) Science)
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Why photoWhy photo--induced structural induced structural dynamics in single crystals?dynamics in single crystals?
Ener
gy
Coordinate
Temperature, Pressure, …
From static to dynamic state
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Toward molecular movieToward molecular moviePump
Probe
‘Watching matter rearrange ’K. Nelson, Science (1999) 286, 1310.
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From static to dynamic studiesFrom static to dynamic studies
X-ray source Synchrotron RadiationX-ray Free Electron Laser
Science Acoustic Phonons
Vibrations (Optical Phonons)
Chemistry & Biology
Electron Dynamics
10-3
milli10-6
micro10-9
nano10-12
pico10-15
femto10-18
attoPulse duration (seconds)
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PhotoPhoto--stationary statestationary state
Photolysis of FePhotolysis of Fe--CO bond in CO bond in hemoglobinhemoglobin--CO CO
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identity: 18 %
Hemoglobin
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What happens when the FeWhat happens when the Fe--CO bonds CO bonds are broken by photoare broken by photo--excitation?excitation?
- Fe -
CO
- Fe -
CO
- Fe -
CO
- Fe -
CO
hν
hν
α
α
β
β
Hemoglobin
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αα subunitsubunit2Fo2Fo--Fc map (1.3Fc map (1.3σσ))
H(F8)
L(F4)
V(FG5)
V(E11)
H(E7)L(B10)
F(CD1)
M(B13)
CO
Haem
H(F8)
L(F4)
V(FG5)
V(E11)
E7HL(B10)
F(CD1)
M(B13)
CO
Haem
Light ON
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αα subunitsubunitFo(light_off)Fo(light_off)--Fo(light_onFo(light_on) map () map (±±3.53.5σσ))
His58
Phe98
His87
Leu29
His89
I (distal)
II (proximal)
III (heme)heme
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αα subunitsubunit ((±±4.54.5σσ))
I.I. distal sidedistal side
His58
His87
Leu29Leu29
CO
His58
His87
4.0
3.4
heme
refined models (light on/off)
Models with d-Fourier map (±4.5σ)Blue (+) : light offRed (-) : light on
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αα subunitsubunit ((±±3.53.5σσ))
II.II. proximal sideproximal side
Phe98
His87
His89
Ala88
Asp85
Leu86F-helix
heme0.31
Models with d-Fourier map (±3.5σ)Blue (+) : light offRed (-) : light on
refined models (light on/off)
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TimeTime--resolved measurementresolved measurement
PhotoPhoto--induced phase transition in induced phase transition in organic charge transfer complex organic charge transfer complex
(TTF(TTF--CA, EDOCA, EDO--TTF)TTF)
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PhotoPhoto--induced phase transitioninduced phase transition
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Laser-induced ferroelectric structural order in TTF-CA crystal(Collet et al. Science 300, 612, 2003)
Mixed stack of Donor (TTF) and Acceptor (CA)Mixed stack of Donor (TTF) and Acceptor (CA)At high temperature At high temperature (>(>82K) Neutral 82K) Neutral At low temperature Ionic At low temperature Ionic
Donor
Acceptor
CA
TTF
Cl
Cl
Cl
Cl
S
S
S
S
Acceptor
… D° A° D° A° (D+A-) (D+A-) (D+A-) D° A° D° A°…
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Gigantic Photoresponse in ¼-Filled-Band Organic Salt (EDO-TTF)2PF6
(Chollet et al. (2005) Science 307, 86.)
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ESRF and PFESRF and PF--ARAR
PF-AR
PF
KEKKEK PFPF--ARAR ESRFESRF
Ring energyRing energy 6.5 6.5 GeVGeV 6.0 6.0 GeVGeV
Beam size at the Beam size at the samplesample
0.26 mm (v)0.26 mm (v)x 0.6 mm (h)x 0.6 mm (h)
0.10 mm (v)0.10 mm (v)x 0.06 mm (h)x 0.06 mm (h)
EmittanceEmittance 290 290 nmradnmrad 3 3 nmradnmrad
Time resolved Time resolved mode/yearmode/year
~5000 hours~5000 hours((100100%%
single bunchsingle bunch))
~1700 hours~1700 hours(~30(~30%%
s.bs.b., 16., 16--bunch, bunch, hybrid)hybrid)
Ring current Ring current Electron/bunchElectron/bunch
6060 mAmA80 80 nCnC
16 16 mAmA40 40 nCnC
Bunch durationBunch duration ~ 100psec~ 100psec ~ 150psec~ 150psec
Beam life Beam life 1515--20 h20 h 66--8 h8 hLinac
KEKB
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PFPF--AR NW2AR NW2(for time(for time--sharing use of timesharing use of time--resolved XAFS and resolved XAFS and
diffraction)diffraction)
PF-AR ring
Undulatorin-vacuum4cm period lenghth
Monochromator5-20keV
Focusing mirror
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PumpPump--probe Xprobe X--ray diffraction at ray diffraction at PFPF--AR NW2AR NW2
X-ray pulse selector crystal
X-raydetector
PUMPLaser pulse
@1kHz~ 1psec
PROBEX-ray pulse
@1 kHz~100psec
Undulator X-ray pulse@794 kHz
RF clock
PF-AR
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Timing diagramTiming diagram
PF-AR
RFAmplifier
RFMaster
Oscillator508.58MHz
Counter1/6
Mode-lockedTi:S laser
Counter1/89600
RegenerativeAmplifier
RFcavity
NW2Undulator
Counter1/640
Counter1/840
84.7MHz 945 Hz
800 nm945 Hz250 fs
LaserBooth
NW2Experimental
Hutch794kHz 945 Hz
794kHz 5-20 keV945 Hz100 ps
X-ray Pulse Selector
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BeamlineBeamline NW2NW2
Electron beam
X-ray beam Laser beam
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FemtosocondFemtosocond laser systemlaser system
MilleniaCW, 532nm, 5W
TunamiTi:SapphireMode locked(Lok-to-Clock)
EvolutionNd:YLF
SpitfireRegenerative amplifier1kHz 780-840nm
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PFPF--AR NW2AR NW2experimental hutchexperimental hutch
X-ray pulse selector
794kHz945Hz(1/840)
Cryogenic N2 flow
Pulse laserMode-locked Ti:S+ regen.
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PFPF--AR NW2AR NW2diffractomatordiffractomator
X-ray pulse
Laser pulse
CCD(RIGAKU/MSCMercury)
Cryogenic N2 flow
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Laser-induced ferroelectric structural order in TTF-CA crystal(Collet et al. Science 300, 612, 2003)
Mixed stack of Donor (TTF) and Acceptor (CA)Mixed stack of Donor (TTF) and Acceptor (CA)At high temperature At high temperature (>(>82K) Neutral 82K) Neutral At low temperature Ionic At low temperature Ionic
Donor
Acceptor
CA
TTF
Cl
Cl
Cl
Cl
S
S
S
S
Acceptor
… D° A° D° A° (D+A-) (D+A-) (D+A-) D° A° D° A°…
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Time course of Time course of diffraction intensitydiffraction intensity
225mW @ 946 HzIn 1mmφ
175mW @ 946 HzIn 1mmφ
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Time course of the distance between Time course of the distance between TTTTF and F and CACA moleculesmolecules
-1500 -1000 -500 0 500 10003.2
3.3
3.4
TTF-CA distance
distance
time / psec
upper below
upper
lower
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A New A New BeamlineBeamline, PF, PF--AR NW14AR NW14fully dedicated to timefully dedicated to time--resolved diffractionresolved diffraction
(funded by ERATO, JST)(funded by ERATO, JST)
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Specifications of NW14Specifications of NW14
ComponentsComponents SpecificationsSpecifications
UndulatorsUndulators Two inTwo in--vacuum, linear polarization vacuum, linear polarization undulatorsundulators ((U36, U20U36, U20))U36U36 λλu:36mm, Number of magnets:u:36mm, Number of magnets:8686, Total length:, Total length:3096mm3096mm
Minimum gap:10mm, Maximum power:3.1kWMinimum gap:10mm, Maximum power:3.1kWU20U20 λλu:u:2020mm, Number of magnets:mm, Number of magnets:7575, Total length:, Total length:1500mm1500mm
Minimum gap:Minimum gap:88mm, Maximum power:mm, Maximum power:0.70.7kWkWFront endFront end PFPF--ARAR standard standard ((same as NW2, NW12same as NW2, NW12))
PrePre--, and Main mask, absorber, beam shutter, graphite filter, slit, , and Main mask, absorber, beam shutter, graphite filter, slit, Be window Be window
OpticsOptics DoubleDouble--crystal crystal monochromatormonochromator (Si(111), liquid nitrogen cooled, (Si(111), liquid nitrogen cooled, 22--25keV)25keV)BentBent--cylindrical mirror (cylindrical mirror (RhRh coated, 1m)coated, 1m)HigherHigher--harmonics cutharmonics cut--off mirroroff mirror ((RhRh coated, 1m x 2)coated, 1m x 2)
Experimental Experimental hutchhutch
3 3 diffractometersdiffractometers (Huber 7(Huber 7--axis, axis, RigakuRigaku CyrindricalCyrindrical Imaging Imaging plate, and plate, and RigakuRigaku MercuryCCDMercuryCCD))
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Two Two UndulatorsUndulators at NW14at NW14
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Virtual view of NW14Virtual view of NW14
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Future viewFuture view
Toward subToward sub--picosecondpicosecond XX--ray sourceray sourceFuture Light Source at KEKFuture Light Source at KEKXX--ray Free electron lasers (DESY TESLA, Stanford LCLS, ray Free electron lasers (DESY TESLA, Stanford LCLS, SPringSPring--8 SCSS), ERL (Cornel CHESS)8 SCSS), ERL (Cornel CHESS)
Toward other materialsToward other materialsOther stronglyOther strongly--correlated electron systems, photocorrelated electron systems, photo--active active proteins proteins ……
Toward other techniques using synchrotron radiationToward other techniques using synchrotron radiationXAFS, photoXAFS, photo--electron spectroscopy, Xelectron spectroscopy, X--ray emission ray emission spectroscopy, single molecule imaging, spectroscopy, single molecule imaging, ……
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CoCo--workers workers
KEKKEK--ERATO collaboration (Core members)ERATO collaboration (Core members)Ryoko Tazaki (ERATO, KEK, Chiba Univ.)Ryoko Tazaki (ERATO, KEK, Chiba Univ.)Shunsuke Shunsuke NozawaNozawa (ERATO, JST)(ERATO, JST)JunJun--ichiichi Takahashi (ERATO, JST)Takahashi (ERATO, JST)Jiro Itatani (ERATO, JST)Jiro Itatani (ERATO, JST)Hiroshi Hiroshi SawaSawa (KEK PF)(KEK PF)Hiroshi Kawata (KEK PF)Hiroshi Kawata (KEK PF)Masahiro Masahiro DaimonDaimon (ERATO, JST)(ERATO, JST)ShinShin--ya ya KoshiharaKoshihara (TITECH, ERATO JST)(TITECH, ERATO JST)
PF Light Source DivisionPF Light Source DivisionTokyo Institute of TechnologyTokyo Institute of Technology
ShinShin--ya ya KoshiharaKoshihara (TITECH, ERATO JST)(TITECH, ERATO JST)Matthieu Chollet (TITECH)Tokushi Sato (TITECH)Ayana Tomita (TITECH)Tadahiko Ishikawa (TITECH)
Univ. Univ. RennesRennes 11Eric Eric ColletColletLaurent Guerin HerveHerve CailleauCailleau
EDOEDO--TTF crystal (Kyoto Univ.)TTF crystal (Kyoto Univ.)Akira Ota Hideki YamochiGunzi Saito
SamSam--Yong Park (Yokohama City Univ.)Yong Park (Yokohama City Univ.)Jeremy R. H. Tame (Yokohama City Jeremy R. H. Tame (Yokohama City Univ.) Univ.) NaoyaNaoya ShibayamaShibayama ((JichiJichi Medical School)Medical School)Yoshitsugu Shiro (RIKEN/SPringYoshitsugu Shiro (RIKEN/SPring--8)8)
Hemoglobin (SPring-8) TTF-CA and EDO-TTF (PF-AR)