Cheiron School, SPring-8, Japan
October 2, 2012

Introduction of myself

Prof. Kiyoshi Uedaat
Tohoku University 䠄Sendai䠅
Institute of multidisciplinary research
for advanced materials
Leadinga research group for electron andmolecular dynamics

Studies on atoms and molecules
using synchrotron radiationand free electron lasers

Atomic and molecular science using
Synchrotron Radiation
Ueda, JPB 36, R1 (2003);
Ueda & Eland, JPB 38, S839 (2005);
Ueda, JPSJ 75, 032001 (2006);
Kabachnik et al. PR 451, 155 (2007).

Kiyoshi Ueda
Institute of multidisciplinary research for advanced materials
Tohoku University, Sendai 980-8577, Japan

Application of the SR-based
experimental techniques to laser
experiments(femtosecond laser and FEL)

Outline㻼㼔㼛㼠㼛㼑㼘㼑㼏㼠㼞㼕㼏㻌㼑㼒㼒㼑㼏㼠

1. Introduction to quantum world
2. Atomic resonant photoemission spectroscopy- Introduction to the quantum interference
3. Vibrationally-resolved core-level photoelectron spectroscopy- Adiabatic approximation and Franck-Condon analysis- Young’s double-slit experiments
4. Multiple-ion momentum imaging- Snapshots of molecular deformation within a few fs
5. Electron-ion momentum imaging- Molecular-frame photoelectron angular distributions
6. Interatomic Coulombic decay
7. Characteristic properties of free electron lasers

When matter is shined by the light, electron isemitted from the surface.

8. Atomic multi-photon processes by FEL: from EUV to X(i) Frequency of the light needs to be larger than Q0.
(ii) Kinetic energy of the electron is determined by thefrequency of the light.
(iii) Number of electrons is proportional to the intensityof the light.

㻱㼕㼚㼟㼠㼑㼕㼚’㼟㻌㼑㼤㼜㼘㼍㼚㼍㼠㼕㼛㼚Light at frequency of Q is considered to be a group ofparticles (photons) and each photon has energy hQ.
An electron gets the energy hQ when it absorb one
photon.
The electron in the matter is bound. For the electron
to be emitted from the matter, the electron needs toreceive the energy more than the work function W.
Then the kinetic energy KE of the emitted electron canbe given as KE = hQ – W.

Photoelectron spectroscopy (UPS, XPS)

Balmer and Rydberg formulae

Precision measurements for kinetic energies of photoelectrons
emitted via Einstein’s photoelectric effects

Kinetic
energyPhotoelectron
spectrum

Vacuum level
Intensity
BindingenergyValence level

Balmer found beautiful regularity in the H spectrum!

㻾㼥㼐㼎㼑㼞㼓㻌㼒㼛㼞㼙㼡㼘㼍䠖

O

c

1

Q

1 ·
§ 1
R¨ 2  2 ¸n' ¹©n㼏㻘㻌㼟㼜㼑㼑㼐㻌㼛㼒㻌㼘㼕㼓㼔㼠㻧㻌㻘㻌㼣㼍㼢㼑㼘㼑㼚㼓㼠㼔㻧㻌㻾㻘㻌㻾㼥㼐㼎㼑㼞㼓㻌㼏㼛㼚㼟㼠㼍㼚㼠㻌㻔㻾㻌㻩㻝㻜㻥㻣㻟㻣㻚㻟㻜㻥㻌㼏㼙㻙㻝㻕

Bohr’s atomic model㻱㼘㼑㼏㼠㼞㼛㼚㻌㼛㼞㼎㼕㼠㼟㻌㼑㼤㼕㼟㼠㻌㼛㼚㼘㼥㻌㼣㼔㼑㼚㻌㼠㼔㼑㻌㼏㼘㼍㼟㼟㼕㼏㼍㼘㻌㼛㼞㼎㼕㼠㼟㻌㼟㼍㼠㼕㼟㼒㼥㻌㼠㼔㼑㻌㼒㼛㼘㼘㼛㼣㼕㼚㼓㻌㼏㼛㼚㼐㼕㼠㼕㼛㼚㻌㼛㼒㻌㼝㼡㼍㼚㼠㼕㼦㼍㼠㼕㼛㼚㻦
2S³ pM dM nh

De Broglie’s matter wave and Bohr’s model
Quantization㸸

0M㻘㻌㼍㼚㼓㼘㼑㻌㼛㼒㻌㼞㼛㼠㼍㼠㼕㼛㼚㻧㻌㼜M㻩㻌㼙㼑㼞 㼐M㻛㼐㼠㻌㻘㻌㼍㼚㼓㼡㼘㼍㼞㻌㼙㼛㼙㼑㼚㼠㼡㼙㻧㻌㼞㻘㻌㼞㼍㼐㼕㼡㼟㻧㻌㼙㼑㻘㻌㼑㼘㼑㼏㼠㼞㼛㼚㻌㼙㼍㼟㼟㻌㻞

2S³ pM dM
0nh

2Srn = nO= nh/p = nh/mv

O h/p㼀㼔㼑㻌㼑㼘㼑㼏㼠㼞㼛㼚㻌㼎㼕㼚㼐㼕㼚㼓㻌㼑㼚㼑㼞㼓㼕㼑㼟㻌㼍㼞㼑㻌㼐㼕㼟㼏㼞㼑㼠㼑㻦n= -hcR/n2

Schrödinger equation of H atom (in atomic units)

Atomic and molecular science now
Target: single atom or molecule; size: ~ 1 Å (= 0.1 nm = 10-10 m)

H(r) = E(r)

1
 2
2n

En

1
r



U (r)

w
wr

i

p

p2
2

T

T  U (r )

H



1 w2
2 wr 2

Hamiltonian
kinetic energy
momentumpotential energy

: wave function
complex number (with phase!)

What photon energies to be used
Electron binding energies (eV)

Vacuum ultraviolet light!

The experiments need
to be in the vacuum!

How to use synchrotron radiation to study atoms and molecules
We use monochromatic synchrotron radiation to excite atoms
and molecules and to study their electronic structures as wellas electron and nuclear dynamics in the excited states.
A single photon should be absorbed by a single atom ormolecule first!

SPring-8 BL27SU
Figure-8 undulator
Linearly polarized light
Horizontal polarization (1st)Vertical polarization (0.5th)
T. Tanaka and H. Kitamura, J. Synchrotron Radiation 3, 47 (1996).

SR

Soft X-ray monochromator
Ion
detector

Hettrick type: varied line spacing plane grating
Mol. Beam

The easiest experiment:
ion yield spectroscopy

10000 - 20000

Energy resolution> 1011 photon/s

Photon Flux

0.15 ~ 2.5 keVEnergy range

H. Ohashi, Y. Tamenori, E. Ishiguro et al. Nucl. Instr. Methods A 467, 533 (2001).

•

Ne 1s total ion yield spectrum
np Rydberg series

Auger decay and Auger electron spectroscopy
photoelectron- n = IP – En = R/(n-)2 : quantum defect

R =13.6 eVIPCore hole lifetime
defines the line width!

6 1+HV + V

V= Vdir+

n

2
n

n

1s

H (hQ-En)/(*n/2)

Vn v 1 /(n  P )3

n= const!

Auger electron

Angle-resolved resonant Auger spectra of Ne at
1s -> 3p excitation

SES2002 analyzer
Electrostatic hemisphericalanalyzer– Mean radius 200 mm– 'E/PE=1/1600(66 meV at pass 100 eV)– MCP+CCD cameraor MCP+Delay line anode2p-2(1D2)3p– Gas cell system
or Doppler-free molecular beamsourceUeda et al. PRL . 90, 153005(2003)P (cos T ) [3 cos T  1] / 2
2or effusive beam + momentum
resolved ion spectrometer

E: asymmetry parameter
Measured angular distributions tell us how theangular momenta are coupled in the atom ,allowing us the spectroscopic assignment !

Prümper et al. PRA 71, 052704,(2005).

Resonant Auger spectra of Ne “between”
1s -> 3p and 1s -> 4p excitations
V v I (0)  2 u I (90)Interference effects between the two paths
D$ =d +
6
i+H
n
D

D

nD
n

VD = _$D_
2p-2(1D2)3p

Hn (hQ-En)/(*n/2)
dD = <g|r|D>
DnD= <g|r|in><in|v|D>
_i>

DnD

_D>
dD

De Fanis et al. Phys. Rev. Lett. 89, 023006 (2002).

|g>

Introduction of molecular world

Sendai City

H<( R, r )
TR



!
w2
¦
2 k Mk wRk2

H

Statue of Load Date

E<( R, r )KE of nucleus

H 0  TR

H0

H TR  Tr  V (r, R)
Tr



!
w2
¦
2m j wrj2

KE of electrons

Tr  V (r , R)

[ H 0  H n ( R )]M ( R, r )0

H n (R ) : adiabatic potential energy< ( R, r ) ¦ ) ( R)M ( R, r )nnn[TR  H m ( R)]) 0mv ( R)0Emv
) 0mv ( R)

Nuclear motion is within the adiabatic potential energy surface!

Born-Oppenheimer approximation
Jozenji Street

Franck-Condon approximation for photoionization

V iv' (E) ~| ³ X iv* ' (R)DE (R) X 0 (R)dR |2

Xiv* ' ( R), X 0 ( R) : Vibrational wavefunctions of ionic iv’ and ground 0 states

DE ( R )³ M ( r , R ) rM
*
E

core

( r , R )dr

M E ( r , R ), M core ( r , R ) : Electronic wavefunctions of the continuum E and core orbitals

Franck-Condon analysis based on harmonic approximation
Linear coupling model
Intensity

Q‘ = 2Q‘ = 1Ionic state

F (1,0)§ D ( 'R ) 2 ·D ( 'R ) 2¸
exp¨¨ 
2
2 ¹¸
©

D

Q‘ 
'R

Assume that the dipole moment DE(R) does not depend on R

V iv' ( E) ~| DE (Re ) |2 F (v'0)
F ( v '0 ) | ³ X iv* ' ( R ) X 0 ( R ) d R |2 Franck-Condon factor

Q=0

Photoelectron
spectrum

F (0,0)PZ !

§ D ( 'R ) 2 ·¸
exp¨¨ 2 ¹¸©

F(1,0) D('R)22
F(0,0)

Electronic
ground state

R0

Vibrational intensity distribution in the photoelectron
spectrum is determined by the Franck-Condon factors

R'0Internuclear distanceOne can extract 'R from photoelectron spectroscopy!

Franck-Condon analysis for the vibrational structureof the C 1s and O 1s mainlines of CO

Satellite spectrum in core-level photoemission in CO,a_\+v_\0!_FC factor\0: v=0 vibrational wave functionin the ground state

HOMO-LUMOSS\+ v: v-th vibrational wave functionin the core-ionized state

Mainline

Stable geometry of the core-ionized state
extracted from the vibrational structure
Exper.

TheoryC 1s-10.028

O 1s-1'Re (Å) 0.037(2)-0.051'Re (Å) -0.051 (1)Matsumoto et al. Chem. Phys. Lett. 417, 89-93 (2006).

Ehara et al. J. Chem. Phys. 125, 114304 (2006).

Franck-Condon analysis of the vibrational structure in
the symmetry-resolved C 1s satellite bands of CO

N(1)Solid lines: measured
symmetry resolved
spectraVertical bars: ab initio
FC factors

Ab initio potential curves

N(2)Electrons also showinterference fringes!

Evidence of the dualityof waves and particles!

Evidence that the light is the wave!

Ab initio FC factors reproduce themeasured vibrational distributions.
Ueda et al., Phys. Rev. Lett. 94, 243004 (2005).

Franck-Condon analysis for the vibrational structureof the N 1s 1Vu and 1Vg mainlines of N2

Cohen-Fano two-center interference
Two 1s ortibals in N2 correspond to Young’s double slits.

2500
2000

CountsMolecular core-level ortibals:

N2 N 1shQ=500 eV

1500

Core-level photoemission from fixed-in-space N2:

1000
500
0

90.0

90.5

Two center photoelectron wave

91.0

Kinetic energy (eV)-1

Relative intensity

(1Vu)
-1
(1Vg)

SAC-CIv’=090.5

Equilibrium geometries of the core-ionizedstates extracted from the vibrational structure

Exper.
N 1Vu-1'Re (Å) -0.023(1)N 1Vg-1v’=1
90.0'Re (Å) -0.018(1)91.0TheoryInterference fringe

where k: photoelectron momentum; R1,R2: position vectors of N (1) and N(2)Orientational average: Cohen-Fano formula-0.021-0.017

Ehara et al. JCP 124, 124311 (2006)

Kinetic energy (eV)Interference oscillatory structure becomes much smaller but remains!
H.D. Cohen and U. Fano, Phys. Rev. 150, 30 (1966).

Ab initio N 1s 1Vu and 1Vg photoionization cross sections of N2

Vg /Vu ratio: experiment vs ab initio and Cohen-Fano
2.2
2.0

Oscillation:
Two-center Interference
Cohen-Fano prediction !

Cross section ratio Vg/Vu

1.8
1.6

N K shell
2/
Experiment
Original Cohen-Fano
RPA

1.4
1.2
1.0
0.8
0.6
1

2

3

4

5

6

Electron momentum (a.u.)
Both experimental and ab initio interference fringes shift from the prediction
by Cohen-Fano formula!
Liu et al., J. Phys. B. 39, 4801-4817 (2006); JESRP 156-158, 73-77 (2007).

Semenov et al., J. Phys. B: At. Mol. Opt. Phys. 39, L261 (2006)

Photoelectron scattering by the neighboring N atom
The amplitude of the photoelectron wave from one center:

A1

B1\ $%

The amplitude of the photoelectron wave from two centers: \ r \

Cohen-Fano interference
A1A2 interference term
N(1)

N(2)

N(1)

N(2)

The cross section~ |\ r \|2| $% r $% |20

A1B1 and A2B2 one-center interference terms

G1(k): scattering phase
CF A1A2 interference term

A1B2 and A2B1 two-center interference terms !

Sendaiin summer

Tanabata festival

Multiple-ion coincidence imaging setup
E fieldhQ

field free
TOF tube

electron
MCPY

Ion 2DPSD

How to obtain 3D momentum
px

x2y2t2
x1y1t1t0

t, Z 80mm
x4y4t4X
x3y3t3supersonic jetm x  x0
, pyt

t: ion time-of-flight
to: ion TOF at restm y  y0
, pztx, y: arrival position on the detector.
x0, y0 : initial position of the ion
m : ion mass
q: ion charge

25

70
skimmer

140 mmC1s

O2s

O+ + CO+4

6

Iterative procedure

To be exact Pz becomes nonlinear

O

Renner-Teller splitting of CO2

C

Out-of-plane 2Su: B1E

CO2 C1s-1 2Su

C2sO
Bending plane ԋ E

In-plane 2Su : A1

O

TIY

O

297.63 eV
C K-edge

C+ + O +E: electric field in the acceleration region
2

TOF of 1st ion (Ps)

Sample gas jet
3D momentum of each particle

position & time of flight (x,y,t)

Total electron yield spectrum of CO2 in the C1s excitation region
CO2 ground state configuration:
1Vg21Vu22Vg23Vg22Vu24Vg2
O1s

3Vu21Su41Sg4(16g+); 2Su05Vg04Vu0
2Su  2Vg resonanceS*

Intensity (arb. units)qE t  t0

6
TOF of 2nd ion (Ps)42

4Vu  2VV
shape
resonance
shaperesonanceu g
CO2 Ground state-Franck-Condon
regionC

E

Bending plane // E

2e exc.

CO23+ -> C+ + O+ + O+
290

295

300

305

310

315

320

325

180º
Bond angle

Photon energy (eV)Snapshot of the bending motion in the core-exited statewith a liftetime ~7 fs
Newton DiagramOut-of-plane 2Su: B1
LinearElectron-ion coincidence momentum imaging
Multihit 2D detector
Y

Electric field

Multihit 2D detector
Y

B+
N

In-plane 2Su : A1
e-

Bent

B+
e- N
A+
O

A+
O

X

X
X-raysMagnetic field

Ion-ion coincidence

Molecular axis

Molecular-frame e- angular distribution

Electron-ion-ion coincidence

Retrieval of the source point

Ion momentum conservation
Muramatsu et al. Phys. Rev. Lett. 88, 133002 (2002).

Towards photoelectron diffraction measurement

Total electron yield spectrum of CO2 in the C1s ionization region

4Vu  2Vg shape resonance

Reaction plane
Reaction plane 㸻plane define by the E vector and molecular axis

CO2 ground state configuration:
1Vg21Vu22Vg23Vg22Vu24Vg2
O1s

C1s

O2s

C2s

3Vu21Su41Sg4(16g+); 2Su05Vg04Vu0

Te-Electric vector

Electron emission
direction

Tn

O

C 1s threshold
297.63 eVCO
Molecular axis

N. Saito et al., J. Phys. B, 36 L25 (2003).

We focus on the electron emission within this reaction planeC1s photoelectron diffraction (MFPAD) of CO2:
comparison between experiment and theory
Photon energy

Near Sendai

Shaperesonance

Motsu-jiMatsushima bay

The general agreement between experiment and theory is reasonable.
At the shape resonance, the intensity drops at Tn 90q i.e. 6-6 paralleltransition. The intensity drops at T 90 q , i.e., Vu photoelectron wave !

Mount Zao

Chuson-ji

Why is ICD important?

Auger vs Interatomic Coulombic Decay (ICD)

ICD: electronic decay where the environment plays a role!
ICD takes place in van der Waals clusters, in hydrogen bonding clusters, inmetallofullerenes, in bio-molecules in the living cell, etc
ICD is everywhere!
ICD is one of the key players in energy and charge transfer in these systems.

Ne

Energy transfer via
virtual photon exchange

Intra-atomic

high-energy Auger e-

low-energy ICD e-

Metal atom in C60

ICD rate is R dependent!

Interatomic Coulombic Decay (ICD)

Observation of ICD in Ne2 by Frankfurt group
Ne2+ (2p-2)

TheoreticalFirst prediction - HF cluster:
L.S. Cederbaum, J. Zobeley, and F. Tarantelli, Phys. Rev. Lett. 79, 4778 (1997).
Prediction - Ne dimer:
R. Santra, J. Zobeley, L.S. Cederbaum et al., Phys. Rev. Lett. 85, 4490 (2000).

60䜶䝛䝹䜼䞊䝺䝧䝹䚷㻔㼑㼂㻕

Ne+ (2s-1)
40

5.16 eVICD Ne+(2p-1) + Ne+(2p-1)
Ne+ (2p-1)

20

Experimental
First observation - Ne cluster:U. Hergenhahn and coworkers, Phys.Rev. Lett. 90, 203401 (2003).

Potential energyAB*(a) (b)KE(e)KER
A+ + B

0R
KE(e)+KER = 5.16 eV

Cluster-size-dependent lifetime:
G. Öhrwall et al., Phys. Rev. Lett. 93, 173401 (2004).
Ne2 e-ion-ion coincidence:
R. Dörner and coworkers, Phys. Rev. Lett. 93, 163401 (2004).

Ne+

Ne+

T. Jahnke et al.
Phys. Rev. Lett.
93, 163401 (2004)

Electron-ion-ion coincidence momentum imaging

Interatomic Coulombic Decay after Auger decay
Prediction - ICD from Auger final states in Ne dimer:
R. Santra and L.S. Cederbaum, Phys. Rev. Lett. 90, 153401 (2003).

Experimental evidence of interatomic Coulombic
decay from the Auger final states in argon dimers(a) Core photoionization and Auger decay

2p ionization

Why is ICD after Auger decay interesting and important?
Radiation damage caused in bio-molecules in the living cell
Auger

Radiation damage, caused by e.g., X-ray radiation, is initiated by core ionization.

(b) Interatomic Coulombic decay

Radiation damage is known to be caused by low energy electron collisions, not high energy
Auger electrons.

ICD electron
virtual photon

ICD is one of the important mechanisms to produce low energy electrons after Auger decay!

SPring-8 view from sky

ICDLabeling electron emission site via the ionic charge state

Morishita et al. Phys. Rev. Lett. 96, 243402 (2006).

(c) Fragmentation[A+(core-1)-A] +e-Photo ! [A2+ - A] +e-Auger ! [A2+ + A+] + e-ICD

Ar2+

Ar+

Is the ICD electron ejected from the A+ site or A2+ ?
Can the A+ or A2+ be which-way information of the double slit experiment ?
We can experimentally answer to this very basic question!

fragmentation
We detect ICD electrons in coincidence with Ar+ and Ar2+
using e-i-i coincidence momentum spectroscopy

Multiple coincidence momentum imaging
Multihit 2D detector
Y

Electric field

Multihit 2D detector
Y

B+
N
e-

B+
e- N
O+
A

A+
O

X

Ar2
TOF of Second Ion (Ps)X

PIPICO spectrum

864
filtering2

X-rays2
4
6
TOF of First Ion (Ps)

Magnetic field

3D momentum of each particle

position & time of flight (x,y,t)

Momentum correlation
among the particles

Multiple coincidence

Filter conditions:
Ar+/Ar+: the sum of the momentumof Ar+ and Ar+ ~ 0
Ar++/Ar+: the sum of the momentumof Ar++ and Ar+ ~ 0

Ar++/Ar+ comes from ICD !?

Selection of Dimer from others !

Momentum conservation

Electron spectrum, KER, and their correlation
Electron spectrum coincident with Ar++/Ar+

Equilibrium distance
3.8 A ++Ar
Ar+

Energy diagram of
the ICD process in Ar2

Coulomb explosion( expected KER ~ 7.6 eV)

Photoelectron ejection(13.4 and 11.3 eV)

KER
Ar++/Ar+

2p-1

Measured KER~ 7.7 eV70

3s-2
3p-33d(䠍P)

KER
A+ + B

KER+ ICD electron= 10 eVR

ICD &fragmentation

CI
3s-13p-1 (䠍P) 10eV

60

AB*

(a) (b)
KE(e)

Ar3+

Auger decay
80

Binding Energy (eV)hv=262 eVphotoionization

Potential energy

3p-1 & 3p-2 (䠍D)

50

3p-2
Breakup following ICD takes placealmost instantaneously.

ICD: KER + KE(ICD electron) ~ constantIslands of slope -1 are ICDs !

40

Ar+

Ar2+

Ar

Ar+

Ar

ICD is very fast!

Ar2+

ICD from the Auger final states in Ne dimerNe+㸩

1s photo-eNe‘direct’ ICD

Variants of ICD‘exchange’ ICD

ETMD

BESSY

Auger
Ne+㸩

Ne㸩

Kreidi et al. J. Phys. B. 41, 101002 (2008).

+2౯

ICD

+1౯
+2౯
+1౯
+1౯
+2౯
Kreidi et al.
Sakai et al
J. Phys. B. 41, 101002 (2008). Phys. Rev. Lett. 106, 033401 (2011).

ICD after Auger decayNe++‘3-electrons’ ICD

Ne+fragmentation
Morishita et al.
Phys. Rev. Lett. 96, 243402 (2006).

We detect ICD electrons in coincidence with Ne+ andNe2+using e-i-i coincidence momentum spectroscopy

Heidelberg U. ICD gangs in Germany and Japan ! AIST

Oichi et al.
Phys. Rev. Lett. 107, 053401 (2011).

EUV-X FELs in the world
LCLS in operation
since2009

Alex
Lenz

2009
Yuichiro

Spas

Norio

Frankfurt U.
SCSS test accelerator in operation
since 2008
Reinhard

Markus

Kathi

Till

HIroshi

Kyoto U.

Tohoku U.

SACLA in operation since March 2012

Swiss FEL (2016), Korean FEL,
Shanghai FEL, etc., are coming!
Hironobu

KentaroGeorg

Xiao-Jing

FLASH in operation since 2005
FERMI starts operation in December 2012!

European XFEL starts operation in 2015?

Kiyonobu

&KDUDFWHULVWLFSURSHUWLHVRI)(/SXOVHVCoherent, intense, and ultra-short pulses
at short wavelengths (EUV to X –rays)
Coherent X-ray imaging of non-crystalized samples&KDUDFWHULVWLFSURSHUWLHVRI)(/SXOVHVIntense and ultra-short pulses at X –rays
Why X-rays? structure determination at atomic resolution
Femtosecond X-ray Protein Nanocrystallography, Chapman et al., Nature 470,
73–77 (2011).

Gösta Huldt, Abraham Szöke, Janos Hajdu (J.Struct Biol, 2003 02-ERD-047)
BeforeDuring ~10 fs

After ~50 fs

Neutze, Wouts, van der Spoel, Weckert, Hajdu Nature 406, 752 (2000)

Single Mimivirus Particles Intercepted and Imaged with an X-ray laser
Seibert et al.
Nature 470, 78–81 (2011)&KDUDFWHULVWLFSURSHUWLHVRI)(/SXOVHV
ultra-short (100 – 10 fs)
Attosecond dynamics

Femtosecond dynamics

0 – 0.5 fs

Mili-second mechanics

0 – 200 ms

High-Resolution Protein Structure Determination by Serial Femtosecond
Crystallography, Boutet et al. Science 337 (6092) 362 (2012).

&KDUDFWHULVWLFSURSHUWLHVRI)(/SXOVHV
ultra-short (100 – 10 fs)
Femtosecond dynamics

Courtesy of Simone Techert

Courtesy of Simone Techert0 – 10 ps

0 – 10 ps

Mili-second mechanics

0 – 200 ms

Catching atomic motion in reaction(molecular movie)

&KDUDFWHULVWLFSURSHUWLHVRI)(/SXOVHVIntense1014 W/cm2 (EUV) - 1020 W/cm2 (X)&KDUDFWHULVWLFSURSHUWLHVRI)(/SXOVHV‫ ۑ‬Short wave-length: toward Hard X-rays
Structure determination at atomic resolution

One LCLS pulse at 2 keV
can remove all ten
electrons from the neonatom.

‫ ۑ‬Coherent
Coherent X-ray imaging of non-crystalized samples‫ ۑ‬Ultrafast 100 -10 fs: resolving atomic motion-> ~ 200 as: resolving electron wave-packet motion

The pulse is so intense thatit causes electronic damage
to the sample.

‫ ۑ‬Intense 1014 W/cm2 (EUV) - 1020 W/cm2 (X)Light matter interaction

Femtosecond electronic response of atoms to ultra-intense
x-raysL. Young et al., Nature 466, 56 (2010).

SACLA (XFEL lased on 7 June 2011)

Non-linear response
Electronic damage
Warm (Hot) dense matter science

SACLA XFEL
Photon energy range: 4-20 keV
Photon numbers:

㹼 1011 photon/pulse (5-15 keV)

Repetition rate: 10~60 Hz

Pulse width 10 ~ 15 fs

 50 nm (0.5 m)

Focusing optics: ~1 µm (1.5 m)

First round user beam time: March – July 2012
My first
beam time:
30 May(RIKEN)– 4 June 2012
Project Leader:
TetsuyaIshikawa
Atoms and atomic clusters

Second round beam time: September 2012-March 2013
My second beam time: 2–5 December 2012
Molecules
on air!

SCSS test accelerator : EUV-FEL (20-24 eV)
Momentum or velocity
imaging apparatus

Multi-photon ionization of atoms‫ ە‬Second-order autocorrelation of SCSS EUVFEL pulses via timeresolved two-photon single ionization of He– Characteristics of SASE-FEL‫ ە‬Photoelectron angular distributions for two-photon Ionization of He
atoms by SCSS EUVFEL pulses– Potential of coherent control via seeded FEL㻃‫ ە‬Deep inner-shell multi-photon absorption of Ar and Xe atoms by
SACLA XFEL pulses– Relevance to the electronic radiation damage

EUV-FELMultiple ionization of rare gas atoms and clusters: with M. Yao’s group
VMI: with help of M. Vrakking’s group
Autocorrelation: with J. Ullrich’s group

Second-order autocorrelation of EUV FEL pulses via
time resolved two-photon single ionization of He

Autocorrelation measurement with He two photon ionization

R. Moshammer, Th. Pfeifer, A. Rudenko, Y.H. Jiang, L. Foucar, M. Kurka, K.U. Kuhnel,
C.D. Schroter, J. Ullrich, O. Herrwerth, M.F. Kling, X.-J. Liu, K. Motomura, H. Fukuzawa,
A. Yamada, K. Ueda, K. L. Ishikawa, K. Nagaya, H. Iwayama, A. Sugishima, Y. Mizoguchi,
S. Yase, Yao, N. Saito, A. Belkacem, M. Nagasono, A. Higashiya, M. Yabashi, T. Ishikawa,
H. Ohashi, H. Kimura, and T. Togashi, Optics Express 19, 21698 (2011).
spike~7 fs

Recoil ion detector
He+

He

FEL
He0

1s2

I2

Y

Split mirror
X

Time difference

Ion yield (counts/shot)broad component ~ 30 fs

㻜㻚㻝

㻜㻚㻜㻝

pulse duration=FWHM/ 2

Split mirror assembly: MPI-K, ASG-CFEL, MPQ
Intensity (arb. units)
Mirror: Mg/Si multilayer (f=600 mm, LBNL)

Optics Express 19, 21698 (2011).

spectral intensity density [arb.u.]
intensity [arb.u.]

1.0

0.5

0.0
59

1.0
0.9
0.8
0.6
0.5
0.4
0.3
0.1
0.0
-0.1
-100

60
61
62
wavelength [nm]SCSSSamplePulseShapes

63

spectral intensity density [arb.u.]
intensity [arb.u.]

-50

0
50
time [fs]

100

1.0

0.5

0.0
60
61
62
wavelength [nm]

-50

63

0
50
time [fs]

-50

0
50
time [fs]

0.5
0.3
0.0
-0.3
-0.5
-0.8

100

-100

-50

0
50
time [fs]Experimental evidence for competition between theresonant and non-resonant two-photon ionization

2.5
2.0
1.5
1.0
0.5
0.0
59
2.5

60
61
62
wavelength [nm]R. Ma, K. Motomura, K.L. Ishikawa, H. Fukuzawa, A. Yamada,
K. Ueda, K. Nagaya, S. Yase, Y. Mizoguchi, M. Yao, A. Rouzee,
A. Hundermark, M. Vrakking, P. Johnsson, M. Nagasono, K. Tono,
T. Togashi, Y. Senba, H. Ohashi, M. Yabashi, and T. Ishikawa
63

2.0

Photoelectron angular distribution for
two-photon single ionization of He

1.5
1.0
0.5
0.0
-100

100

0.8

0.5
0.3
0.0
-0.3
-0.5
-0.8
-100

59

1.1
1.0
0.9
0.8
0.6
0.5
0.4
0.3
0.1
0.0
-0.1
-100

0.8
electric field [arb.u.]electric field [arb.u.]spectral intensity density [arb.u.]
intensity [arb.u.]electric field [arb.u.]

-50

0
50
time [fs]

-50

0
50
time [fs]FEL
Velocity Map Imaging(VMI) spectroscopy

100

Direct numerical simulation of the two-electron
time-dependent Schrödinger equation (TDSE)

1.0
0.8
0.5
0.3
0.0
-0.3
-0.5
-0.8
-1.0
-100

100

vs

MCP +
PhosphorscreenCCD
camera100

Excitation energies for two-photon ionization of He

Photoelectron angular distribution for two-photon ionization of He
20.3 eV21.3 eV23.0 eV24.3 eV

Photon energy range available at SCSS test accelerator
Resonant

Resonant

Coherent excitationof Rydberg manifold

Coherent excitationof Rydberg manifold

Resonant

Red lines:
Measured PADs
Blue lines:
Results of the TDSE
calculations

Resonant

Nonresonant

Nonresonant

W. F. Chan et al., Phys. Rev. A 44, 186 (1991).

R. Ma, K. Motomura, K. L. Ishikawa, H. Fukuzawa et al., submitted.

Photoelectron angular distribution for two-photon ionization of He
V
outgoing photoelectron wave is>1  E 2 P2 (cos T )  E 4 P4 (cos T )@ aThesuperpositionof s and d waves.
I (T )

4S

Anisotropy parameters

c /c

W

10 ª 1 Wº
cos G » E 4
W 2  1 ¬« 7
5
¼,

E2

0

2

: Amplitude ratio ,G

18
7(W 2  1)

G G
0

2

see:
K. L. Ishikawa and K. Ueda,
Phys. Rev. Lett.,
108, 033003 (2012).

: Phase difference

Deviation from scattering phase shift difference#The excitation laser is a shortpulse with finite width in both
energy and time!
Taking it into account, we haveG

Gien, J. Phys. B, 35, 4475 (2002).

Additional
G SC  Arg c0 / c2 phaseshiftSC : scattering phase shift difference

cl : complex amplitude of a final state with an angular momentum l
l : phase of each partial wave

K. L. Ishikawa and K. Ueda,
Phys. Rev. Lett., 108, 033003 (2012).

W
off-resonanceon-resonance

T: the pulse width

Deviationfrom  isevidenceof competition. Realand imaginaryparts
of c correspondto theSClbetweenand non-resonant
pathsyresonant
andresonant
non-resonant
paths, respectivel
Tailoring continuum wavepacket controlling theadditional phase shift by the short EUV pulses !

Dependence of W and  on the pulse width of
the Fourier transform limited pulse

Multiple ionization of rare gas atoms irradiated by EUV
free-electron laser pulses at 51 nm
K. Motomura, H. Fukuzawa, K. Papamihail, M. Kurka, A. Rudenko, L. Foucar,
H. Iwayama, K. Nagaya, X.-J. Liu, H.-U. Kühnel, G. Prümper, P. Labropoulos,
J. Ullrich, K. Ueda, N. Saito, H. Murakami, M. Yao, A. Belkacem, R. Feifel,
M. Nagasono, A. Higashiya, T. Togashi, H. Ohashi, and H. Kimura, M. Yabashi,
and T. Ishikawa
Ar 7+ > 434 eV> 18 photons

Kr 8+ > 508 eV> 21 photons

T: the pulse width

Chirping the pulse width from 500 as to 20 fs, we can control
the contributions of direct and non-direct contributions
Tailoring the continuum wave packet (wave function)!
Ishikawa and Ueda, PRL 108, 033003 (2012).

Mirror:Mg/Si multilayer
f=250 mm,made by LBNLDeep inner-shell multiphoton absorption of Ar and Xe
by SACLA XFEL pulses

Time of Flight spectrum of argon ions
KLL->2LMM

XFEL
Ar jettheorists

experimentalists

XFEL fluence dependence for Arn+ yields

Charge state distribution of Ar: experiment and theory

1

10

p=1

Ion yield (counts/shot)

Ion yield (counts/shot)

4+

Ar

0

10

3+

Ar
-1

10

p=2

8+

Ar
-2

10

0

10

-1

10

-2

10

-3

10

9+

Ar

1

2

Experiment
2
Theory (40 PJ/Pm )2
Theory (70 PJ/Pm )2
Theory (100 PJ/Pm )

3

4

5

6

7

8

9

10

Charge state

-3

10

40

60

80

100

120

In the theory, the pulse shapeof Gaussian of 30 fs (FWHM),
and Gaussian focal shape of
1 m (FWHM)1 m(FWHM) are assumed.

2

Peak fluence (PJ/Pm )By comparison with theory,
we obtained peak fluence of
70 J/m2 in the experiment.

Time of Flight spectrum of xenon ions

Experiment done at 5.5 keV, at SACLA !

XFEL fluence dependence for Xen+ yields

Xenon ion charge distributions (exper. vs theory)

Experiment done at 5.5 keV, at SACLA !

Xenon ion charge distributions (exper. vs theory)

0

10

-1

10

Ion yield (counts/shot)

p=1

8+

Xe

-2

10

p=

2

14+

Xe

-3

10

18+

Xe
-4

10

p=

3

One photon
absorption
24+

Xe

Two
photonThreephoton4

Four
Photon!

=
p
-5

10

10

100
2

Peak fluence (PJ/Pm )Xe atoms can absorb more than one x-ray photons!
Experiment done at 5.5 keV, at SACLA !

Relevance to other fields: Radiation damage
Radio-sensitizer

Anomalous X-ray scattering

Deep inner-shell multiphoton ionization by intense x-ray
free-electron laser pulses
H. Fukuzawa, S.-K. Son, K. Motomura, S. Mondal, K. Nagaya,
S. Wada, X.-J. Liu, R. Feifel, T. Tachibana, Y. Ito, M. Kimura,T. Sakai, K. Matsunami, H. Hayashita, J. Kajikawa, P. Johnsson, M. Siano, E. Kukk, B. Rudek, B.
Erk, L. Foucar, E. Robert,
C. Miron, K. Tono, T. Togashi, Y. Inubushi, T. Sato, T. Katayama,
T. Hatsui, T. Kameshima, M. Yabashi, M. Yao, R. Santra,
and K. Ueda (submitted)

5Br-Uracil
I

Multiwavelength anomalous diffraction at high X-ray intensity

5I-Uracil

S.-K. Son, H. N. Chapman, and R. Santra,
Phys. Rev. Lett. 107, 218102 (2011).

The endThank you very much foryour attention!

A couple postdoc positions are open at
Tohoku University for SACLA project!