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

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

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)

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

Toward molecular movieToward molecular moviePump

Probe

‘Watching matter rearrange ’K. Nelson, Science (1999) 286, 1310.

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)

PhotoPhoto--stationary statestationary state

Photolysis of FePhotolysis of Fe--CO bond in CO bond in hemoglobinhemoglobin--CO CO

identity: 18 %

Hemoglobin

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

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

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

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

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)

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)

PhotoPhoto--induced phase transitioninduced phase transition

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°…

Gigantic Photoresponse in ¼-Filled-Band Organic Salt (EDO-TTF)2PF6

(Chollet et al. (2005) Science 307, 86.)

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

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

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

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

BeamlineBeamline NW2NW2

Electron beam

X-ray beam Laser beam

FemtosocondFemtosocond laser systemlaser system

MilleniaCW, 532nm, 5W

TunamiTi:SapphireMode locked(Lok-to-Clock)

EvolutionNd:YLF

SpitfireRegenerative amplifier1kHz 780-840nm

PFPF--AR NW2AR NW2experimental hutchexperimental hutch

X-ray pulse selector

794kHz945Hz(1/840)

Cryogenic N2 flow

Pulse laserMode-locked Ti:S+ regen.

PFPF--AR NW2AR NW2diffractomatordiffractomator

X-ray pulse

Laser pulse

CCD(RIGAKU/MSCMercury)

Cryogenic N2 flow

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°…

Time course of Time course of diffraction intensitydiffraction intensity

225mW @ 946 HzIn 1mmφ

175mW @ 946 HzIn 1mmφ

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

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)

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))

Two Two UndulatorsUndulators at NW14at NW14

Virtual view of NW14Virtual view of NW14

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, ……

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)