Interaction Visualization among Molecules and Atoms
by Synchrotron Radiation– Electrostatic Potential and Electric Field Imaging
in Materials by MaxEnt Analysis –Masaki Takata
RIKEN/SPringRIKEN/SPring-8, JASRI/SPringJASRI/SPring-8, The University of Tokyo,

The MEM charge density studies
with nano-applications

O2 in Coordination Polymer
Science, 298 (2002), 2358
La2 in C80
Angew. Chem. Int’l Ed.
40 (2001) 2998

SPring-8

Sc2 in C66
Nature, 408 (2000) 426

H2 in Coordination Polymer
Angew. Chem. Int. Ed. 44 (2005) 920

1MEM applications to crystallography
Virtual Diffraction Microscopy

Gas Molecule Imaging adsorbed
adsorbedin nano porous coordination polymer

Diffraction Data Imaging
By Maximum Entropy Method

High Brilliance
Synchrotron Radiation XX-ray

O2Science, 298 (2002), 2358

Diffraction Data

Novel functional materials design by adsorption
Bonding Nature Imaging of Cytochrome c553

Charge Order Imaging of EDOEDO-TTF

Metal

C2H2
Nature 436 (2005) 238

N2
N3 Fe

Insulator
Angew. Chem. Int’l Ed. 43 (2004) 3670

Structure property relationship Imaging

N4

RF=2.2% d >1.6Å
>1.6Å

N1Protein function ImagingSynchrotron Radiation + MEM
Precise Diffraction Data
MEM/Rietveld
MEM/Rietveld Method
To see Bonding Nature
Precise Charge Density Mapping
To see Molecular Interaction
Electrostatic Potential /Electric Field Imaging

2Outline
1.

Charge Density Mapping by MEM/Rietveld
MEM/Rietveld Method

2.

Electrostatic Potential and Electric Field Imaging by MEM

3．

Progress in Measurement Technique @ SPringSPring-8

3-0. TopTop-up mode operation for reliable data taking
3-1. New Single Crystal Diffractometer at BL02B1
3-2. X-ray Pinpoint Structural Measurement

The Large Debye-Scherrer Camera
at SPring-8 BL02B2
SPring-8

Imaging Plate
Collimator

2θShutter
Ion ChamberX-rayωSample3

Si(NIST) Powder Diffraction DataIntensity (Arb. Unit)(λ=0.4Å, Exposure Time: 20min.)

Rwp= 5.2%
RI = 2.5%

2θ (degree)

Si & Diamond MEM Charge Densities
Based on BL02B2 Powder Diffraction Data(100K)

Si0.55 e/Å3C

1.62 e/Åe/Å3

0.0～2.0 0.1[e/Å3]step4

Comparison with Theoretical Charge Density
MEM can visualize meaningful precise charge density by reliable data.

Si Valence Electron Density
Si

MEM Charge Density

First Principle Calculation
Wien 2000

MEM Charge Density

Electrostatic potential

Electrostatic Potential:Ztρ (r )−∫dr '| r − r '|t | r − l − Rt |U (r ) = U nuc (r ) + U ele (r ) = ∑ ∑lU nuc (r ) U ele (r ) ; diverge to ∞1210observed
MEM

864

20
0

0.5

1

1.5

2

2.5

35

Electrostatic Potential Formalism
based on MEM
Phys. Rev. B, 74 (2006)172105

U (r ) = 4π ∑∑ZeProf. Hiroshi Tanaka−|G |2 /η 2tt

Ge − iGR t − FMEM (G ) iGr
Zte + ∑∑erfc(η | r − l − Rt |)Ω | G |2|r−l− Rt |lt

Electron charge contribution term
MEM

Nuclear charge contribution term
Ewald’
Ewald’s Technique

MEM Electrostatic Potential Imaging
PbTiO3

NaClClNa+PbOOTi

0.86e/Å30.25e/Å3-0.9e/Å～0.9e/Å

-0.2e/Å～0.0e/Å

Electric Field Imaging by MEM(F (G ) − ∑ Z e e )e G
∂U ( r )E (r ) = −= 4πi∂r∑
G−|G |2 /η 2MEMtt− iGRtiGr

Ω|G ||G |⎞ r − l − Rt
⎛ erfc(η | r − l − Rt |) 2η e⎟+ ∑∑ Z t ⎜+2⎟
⎜rlRrlR||||−−−−πtltt ⎠ | r − l − Rt |⎝−η 2 |r − l − Rt |2-0.9e/Å～0.9e/Å

PbTiO3

PbPbOOTi

O
0.86e/Å3ED

atomic level
polarization

R.E.Cohen
Nature 385,136(1992）

PbTiO3

EP & EF

6

Polarization of Electronic Charge
in PbTiO3
Ab-Initio Calculation(Valence Electron)Pb

MEM EPMEM Electrostatic Potentialz-component EF amplitude& Electric Field

Pb

O2

R.E.Cohen
Nature 385,136(1992)

Applications to Manganites

Dr. K.Kato

Finding Charge Order inManganite

A-type (NdSr2Mn2O7)

Prof. Y.Moritomo

C-type (Nd0.35Sr0.65MnO3)

CE-type (Nd0.5Sr0.5MnO3)

7

Charge Order Visualization
Half‐doped Manganite: Nd1/2Sr1/2MnO3
Mn4+
Mn3+

d(3x2-r2)d(3y2-r2)

Mn4+

18 K

Resistivity vs. Temp.
H. Kuwahara et al., Science, 270 (1995) 961.

300 K
Mn3.5+

Mn3+

Mn3.5+

Mn4+

Mn3.5+

Mn3+‐1.0+0.5+2.0 e/Å

K. Kato et al., Phys. Rev. B (Rapid Comm.), in press.

Charge Order Visualization
Half‐doped Manganite: Nd1/2Sr1/2MnO3
Mn4+d(3x2-r2)

Mn3+d(3y2-r2)

Mn4+

18 K

Resistivity vs. Temp.
H. Kuwahara et al., Science, 270 (1995) 961.

300 K
Mn3.5+Mn3+Mn3.5+Mn4+Mn3.5+Mn3+

Electrostatic potential on 0.8 e/Å3 iso‐surface‐1.0+0.5+2.0 e/Å

K. Kato et al., Phys. Rev. B (Rapid Comm.), in press.

8Application toNano-Porous Coordination PolymerProf. S.Kitagawa

To see mechanism of gas adsorption

Prof. H.Tanaka

in nano space
O2 in CPL-1

C2H2 in CPL-1

Science 298 (2002) 2358

Nature 436 (2005) 238

MEM Electrostatic Potential in Nano Porous
Electrostatic Potential
Before Adsorption-0.66 eÅ-1 ～ -0.50 eÅ-1
step 0.01 eÅ-1

CuONCH

Local minimum area

O2 adsorbed CPL-1

Local maximum area

C2H2 adsorbed CPL-1

O2C2H2180.1 eÅ-2 ～ 1.0 eÅ-2 step 0.1 eÅ-2

9Complementary Information from X-ray & Neutron
for Atomic Interaction

ingndoBDiffraction Data
X-ray data
Visualization

Electron Desnity

MEMingndoB

Neutron data

Nuclear Density

MEM is efficientfor imaging of interaction
between the atoms and molecule.

10For Reliable DATA Measurement
SPring-8 Top-up Mode Operation
Every second injection
Current stability 0.1%
Invisible Injection!
Increase thermal stability of X-ray optics
Extremely high stability of X-ray beam
Eliminate an incident X-ray monitoring
for both position & intensity

2004.Jan.30th0.2Å Resolution Single Crystal Diffractometer‐Direct Visualization of Charge & Orbital‐@ BL02B1/SPring‐8Prof. H.SawaH.Sawa

Cylindrical Image-Plate

X-ray

1/4χ-goniometer- For
data completenessclose to 100%.
Single axis goniometer- for cryostat andspecial sample chamberon phi-axis for in-situ observation
Specification:
Dynamic range:
Camera radius:
Detector area:2θ coverage:< 106 counts
191.3 mm683(W) x 350(H) mm-60.0 ～ 144.0°

DyMnO311

A Goal of SR Structural Materials Science
Pulse Characteristic
Time Resolved Experiment

For
Much sharper informationof chemical reaction+Narrow directional Characteristic
SubSub-micron Beam Experiment

Ultimate utilization of Synchrotron Radiation

SPringSPring-8

X-ray Pinpoint Structural Measurement.
CREST(Core Research for Evolutional Science & Technology)/ JST（JST（Japan Science & Technology agency)＠agency)＠SPringSPring-8 BL40XU
2004～
2004～2008
Development of the spatialspatial- and timetime-resolved
structural study techniquefor nanonano-materials and devices.
Up to 100nm scale & 40psec

huSingle Crystal Diffraction
From Single Powder Particle
Ｓｉｎｇｌｅ Ｃｒｙｓｔａｌｌｉｎｅ Sｉｚｅ<ｉｚｅ< 1 μm

SRPulse Laser

Ｒａｔｉｏ ｏｆ ＰＩＰ~
ＰＩＰ~ 100%!!
DVD Recording
Mechanism

Undulator

CrystalMechanicalShatter
FZP～70nm beam size

IP DetectorAmorphous

12The TimeTime-Resolved XX-ray Diffraction Profile &The TimeTime-Evolution of Diffraction Intensity and Reflectivity
Applied Physics Express 1, 045001 (2008)(a) GST

Disc Image(b)AIST-

200

102

Intensity [arb. units]

220-Crystal

104 210 Crystal

1 μs

1 μs

400 ns152 ns

172 ns135 ns108 ns0 ns
Amorphous

152025110 ns
96 ns
0 ns
Amorphous

30 15

2θ [deg.]
Intensity [arb. units]

Pump& ProbeMeasurement

300 ns

300 ns20(c) GST 300 ns 400 ns (d)AIST
172 ns135 ns108 ns0 ns0152 ns
110 ns
96 ns0 ns30

400300 ns-102104, 210
reflectivity

200220reflectivity

200252θ [deg.]

0200

Time [ns]MCS
Measurement

400

Time [ns]Pinpoint Structure Measurement Group
Total System Design & Application Team

M.Takata
GL/TL
RIKEN/JASRITokyo Univ.

S.Kohara
ＪＡＳＲＩ

N.Yasuda
ＪＡＳＲＩ

T.Matsunaga
N.Yamada
Matsushita Co. Matsushita Co

M.Nakata
NEC Co.

Time Resolved Measurement Team
Applied Field Structural Study TeamY.Tanaka
TL
RIKEN

Y.Moritomo
TL
Tsukuba Univ.

Y.Fukuyama
Postdoc.

Y.OhishiＪＡＳＲＩ

Sub-micron Crystal Diffraction Team

K.Toriumi
TL
Hyogo Pref.
Univ.

Y.Kuroiwa
Hiroshima
Univ.

Y.Nogami
OkayamaUniv.

Y.Ozawa
Hyogo Pref.
Univ.

H.Ohsumi
RIKEN

K.KatoＪＡＳＲＩ

J.Kim
Postdoc.

X-ray Microbeam Team

S.Kimura
TL
ＪＡＳＲＩ

H.Tajiri
ＪＡＳＲＩ

13SR & Neutron can complementary
visualize an interaction
between atoms and molecules

Thank you!

NANO Road to SR

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