ction ours, Resonant Diffraction on Powders -Site

$Page 1: ction ours, Resonant Diffraction on Powders -Site$
Resonant Diffraction on Powders

-Site SelectiveSpectroscopy

-ChemicalSelectiveDiffraction

H. Palancher, S. Bos, Ch. Pichon, J. Lynch, B. Rebours,

E. Lorenzo, J.-F. Berar, J.-L. Hodeau

Lab. Cristallographie-CNRS-GRENOBLE -(F)

& experimentsattheESRF -GRENOBLE -(F)

Introduction

Application usingResonantDiffraction

-so

me

ba

sis

of

reso

na

nt

diff

ract

ionOutline

DAFS,DANES

� ��ch

arg

e o

rde

rin

La

4M

n5

Si4

O2

2 p

ow

de

rvi

a-“site selective f’ refinement”

.AnisotropyofResonantDiffraction,

� ��si

te s

ymm

etr

y in

form

atio

n :

no

t o

n p

ow

de

rs

SelectiveSite Spectroscopy

ChemicalSelectiveDiffraction

MAD, SAD,

� ��p

ha

se o

fst

ruct

ure

fa

cto

rsResonantContrastDiffraction,

� ��d

ire

ct lo

caliz

atio

no

fa

tom

sin

ze

olit

es

via

-“anomalous differential patterns”,

-“dispersive difference maps”.

_________________________________________________________________________


LLB-SOLEIL march 2006 [email protected]

““Distribution spectrale dans les régions d’absorption propres de

Distribution spectrale dans les régions d’absorption propres de divers cristaux

divers cristaux””

Y.

Ca

uch

ois

, C

om

pte

Re

nd

us

Aca

d.

de

s S

cie

nce

s, C

RA

S,

24

2,

10

0 (

1Y

. C

au

cho

is,

Co

mp

te R

en

du

s A

cad

. d

es

Sci

en

ces,

CR

AS

, 2

42

, 1

00

(1

95

6)

95

6)

““…

l'a

pp

ari

tion

po

ssib

le,

a c

ôté

de

ra

ies

bla

nch

es,

de

ra

ies

no

i…

l'a

pp

ari

tion

po

ssib

le,

a c

ôté

de

ra

ies

bla

nch

es,

de

ra

ies

no

i re

s …

res

…””

““…

Ce

s a

no

ma

lies

d'in

ten

sité

, d

iffé

ren

tes

d'a

bso

rptio

ns

ba

na

les,

…

Ce

s a

no

ma

lies

d'in

ten

sité

, d

iffé

ren

tes

d'a

bso

rptio

ns

ba

na

les,

se

mb

len

t a

ttri

bu

ab

les

au

se

mb

len

t a

ttri

bu

ab

les

au

co

mp

ort

em

en

t e

xce

ptio

nn

el d

es

fact

eu

rs d

e s

tru

ctu

re d

an

s le

s ré

gco

mp

ort

em

en

t e

xce

ptio

nn

el d

es

fact

eu

rs d

e s

tru

ctu

re d

an

s le

s ré

gio

ns

"an

om

ale

s" …

ion

s "a

no

ma

les"

…””

Bra

gg

B

rag

g i

nte

nsi

tyin

ten

sity

En

erg

yd

isp

ers

ive

sp

ect

raw

itha

be

nt

crys

tala

na

lyso

r(M

ica

)E

ne

rgie

: A

l K-

ed

ge

,

Re

flect

ion

(00

2)

HistoricMeasurement

_________________________________________________________________________



Intensity∝ ∝∝∝structurefactor square modulus

Re

son

an

tD

iffra

ctio

n:

Diff

ract

ed

inte

nsi

tym

ea

sure

me

ntversus

the

en

erg

yn

ea

rth

ea

bso

rptio

n e

dg

eo

f a

na

tive

ato

m

Absorption�

loca

l en

viro

nm

en

to

f a

bso

rbin

ga

tom

s

Diffraction �

crys

tallo

gra

ph

icst

ruct

ure

FQ,E

()=

f iQ,E

()

i∑expiQ

.ri

()exp−BiQ

2(

)(

)()

()

()

Eif

Ef

fE

fi

ii

i"

',

0+

+=

QQ

f" (électrons)

f’ (électrons)

0246

-10

-8-6-4-20

64

00

65

00

66

00

67

00

68

00

69

00

70

00

Energie (eV)

Anomalousscatteringfactors

''

)'("

.2

)('

0

22

dE

EE

EfE

Ef

∫∞

−=π

f 0T

ho

mso

n s

catt

eri

ng

am

plit

ud

e

f "(E)

pro

po

rtio

na

ltoE.µ(E)

f '

Kra

me

rs-K

ron

igre

latio

n�f

"

� ��

Relation betweeninte

nsitiesand

f’(E), f’’(E)

_________________________________________________________________________



FQ,E

()=

f iQ,E

()

i∑expiQ

.ri

()exp−BiQ

2(

)

FN

no

n a

no

ma

lou

sa

tom

sFA

an

om

alo

us

ato

ms

∆Φ

∆Φ∆Φ

∆Φ= Φ

T-ΦA

� ��I(h, λ) = Abs.LP.λ3 .(IFTI2+(f

' A2 +

f"A2 )

IFA

I2/f

oA2 +2

IFTIIFA

I(f' Acos(∆Φ

∆Φ∆Φ

∆Φ)+

f"Asin(∆Φ

∆Φ∆Φ

∆Φ))/f

oA)

F

F’

F” A

F

FN

Im

Re

A

F T

FA0

A

Intensity∝ ∝∝∝

structurefactor square modulus

f iQ,E

()=f 0i

Q()+f i'E()+if i"E()

ΦA

∆Φ

∆Φ∆Φ

∆Φ= Φ

T-ΦA

ΦT

Relation betweeninte

nsitiesand

f’(E), f’’(E)

_________________________________________________________________________



ba

sed

on

stru

ctu

refa

cto

r se

lect

iviti

es

we

can

com

bin

e d

iffra

ctio

n a

nd

sp

ect

rosc

op

yin

form

atio

n

� ��SelectiveSite Spectroscopy: DAFS, DANES

DAFS, DANES

� ��Anisotropyof ResonantScattering

FQ,E

()=

f iQ,E

()

i∑expiQ

.ri

()exp−BiQ

2(

)

Chemicalselectivity

Site selectivity

we

can

vary

the

con

trib

utio

n o

f o

ne

spe

cific

ato

mo

n d

iffra

cte

din

ten

sity

� ��Structure Factor Phase Solution : MAD

MAD

� ��ElementSelectiveDiffraction : Contrast

Contrast


_________________________________________________________________________



� ��sameFourier transform

� ��Site selectivedistance information

(on

lyd

iffe

ren

tp

ha

se s

hift

s fo

r D

AF

S o

r X

AF

S)

Cu(111) and (222) Bragg reflections

H.

Str

ag

ier

et

al.

PR

L 6

9,

30

64

(1

99

2)

Site SelectiveSpectroscopy: DAFS

XAFS : atomselectivelocal information

DAFS : atomand site or phaseselectivelocal information

_________________________________________________________________________



DAFS methodon multilayers

� ��Irbufferand Ir/Fe multilayer: differentDAFS signals

� ��selectiveof Irbufferand Ir/Fe multilayer

H.

Re

ne

vie

re

t a

l., P

hys

ica

B 2

08

-20

9,

21

7,

(19

95

)

F.T.

�

MultilayerBragg intensityatIrLIII edge

Irbuffer& Ir/Fe multilayerBragg reflections

Site SelectiveSpectroscopy: DAFS

_________________________________________________________________________



H.

Re

ne

vie

re

t a

l., P

RL

78

, 2

77

5,

19

97

� ��firstneighborshellsof Fe attheIr-Feinterfaces

FQ,E

()=

f iQ,E

()

i∑expiQ

.ri

()exp−BiQ

2(

)� ��Chemical& site selectivities:via s

tru

ctu

re f

act

or

con

trib

utio

ns

Chemicalselectivity

Site selectivity

0123456

65

00

65

50

66

00

66

50

67

00

Mn

OM

n2O

3

Mn

O2

Energie (eV)

DANES

EDAFS

SEUIL

Study of sites with different valence

Valence

sen

sitiv

ityo

fR

eso

na

nt

Diff

ract

ion

d

ue

to

XA

NE

S

sen

sitiv

ityo

ff’

& f ’’

Energyshift ofµ µµµ,

f ’ &

f ’’

_________________________________________________________________________



Mn3

Mn3

Mn1

Mn1

ac

La

La

SiSi

La

4M

n5S

i 4O

22

kno

wn

stru

ctu

re

�Whichvalence state for thethreesites ?

Mn4+�

Mn

1,

Mn3+�Mn2

,

Mn2+�Mn3

0246

-8-6-4-2

6450

6500

6550

6600

6650

Mn

OM

n 2O

3

Mn

O 2

La 4

Mn 5

Si 4

O22

MnO

Mn2O

3

MnO

2

La4M

n5Si4

O22

Mn2

Mn2

Chemicalselectivity

for Valence studies

f' et f'' variation close to theedge

Refinementoff’ (andf’’ usingKK)

Mnvalence statesonLa4Mn5Si 4O22powder

FQ,E

()=

f iQ,E

()

i∑expiQ

.ri

()exp−BiQ

2(

)f i

Q,E

()=f 0i

Q()+f i'E()+if i"E()

_________________________________________________________________________



Me

asu

rem

en

to

f completespectra

(BM

16

-ES

RF

)

-la

rge

an

gu

lar

do

ma

in2θ θθθ

(ex

:50°)

-21

en

erg

ies

dis

trib

ute

da

rou

nd

the

Mn

K e

dg

e(6

53

9 e

V)

�In

tég

ratio

n o

f d

iffra

cte

dre

fect

ion

sC

on

tinu

ou

ssc

an

of diffractedpeaksversusenergy

(BM

2-E

SR

F)

-m

osa

ïca

na

lyse

r (0

.2°)

-b

ack

gro

un

d &

flu

ore

sce

nce

me

asu

rem

en

ts-

sam

plin

gin

ω:

"ωsc

an

s"

�co

ntin

uo

us

sca

ns

of

9 r

efle

ctio

ns

: 6

45

0 <

E <

67

50

eV

Conclusion on theexperimentalstrategies

:�

con

tinu

ou

se

ne

rgy

sca

ns

I(E

)�

be

tte

ra

ccu

racy

�co

mp

lete

spe

ctra

me

asu

rem

en

ts(3

en

erg

ies)

�a

na

lysi

so

f re

flect

ion

sha

pe

sa

nd

sa

mp

ling

0

50

10

0

15

0

20

0

25

0

00,5

11,5

22,5

33,5

64

50

65

00

65

50

66

00

66

50

Raie (0 0 2)

(2)

(1)

Energie (eV)

02468

10

00,5

11,5

2

64

50

65

00

65

50

66

00

66

50

Raie (2 0 -3)

(2)

(1)

Energie (eV)

Differentstrategiesfor DANES measurementson powders

_________________________________________________________________________



I obs

I calc

10

20

30

40

50

60

70 65

20

65

40

65

60

65

80

66

00

66

20

Energie (eV)

Intensité (u.a.)

Raie (0 0 1)

10

0

12

0

14

0

16

0

18

0

20

0

22

0

24

0

26

0 65

20

65

40

65

60

65

80

66

00

66

20

Energie (eV)

Intensité (u.a.)

Raie (0 0 2)

3456789

10 65

20

65

40

65

60

65

80

66

00

66

20

Energie (eV)

Intensité (u.a.)

Raie (2 0 -3)

25

30

35

40

45

50

55 65

20

65

40

65

60

65

80

66

00

66

20

Energie (eV)

Intensité (u.a.)

Raie (3 1 -1)

Re

fine

me

ntoff’ resonantscatteringfactorsfor the

3 M

nsi

tes

usi

ng

kno

wn

crys

talli

ne

stru

ture

S.

Bo

se

t a

l., u

np

ub

lish

ed

_________________________________________________________________________



I obs

I calc

S.

Bo

se

t a

l., u

np

ub

lish

ed

_________________________________________________________________________



25

30

35

40

45

50

55 65

20

65

40

65

60

65

80

66

00

66

20

66

40

Energie (eV)

Intensité (u.a.)

Raie (0 0 3)

8

10

12

14

16

18 65

20

65

40

65

60

65

80

66

00

66

20

66

40

Energie (eV)

Intensité (u.a.)

Raie (1 1 -4)

8

10

12

14

16

18 65

20

65

40

65

60

65

80

66

00

66

20

66

40

Energie (eV)

Intensité (u.a.)

Raie (2 0 -4)

40

50

60

70

80

90 65

20

65

40

65

60

65

80

66

00

66

20

66

40

Energie (eV)

Intensité (u.a.)

Raie (4 0 0)

Re

fine

me

ntoff’ resonantscatteringfactorsfor the

3 M

nsi

tes

usi

ng

kno

wn

crys

talli

ne

stru

ture

-12

-10

-8-6-4-2

64

80

65

20

65

60

66

00

66

40

66

80

67

20

Mn

1M

n2

Mn

3f'_

Sa

s

Energie (eV)

f' (électrons)

Re

fine

me

ntofresonantscatteringfactorsfor the

3 M

nsi

tes

S.

Bo

se

t a

l., u

np

ub

lish

ed

012345678 65

00

65

20

65

40

65

60

65

80

66

00

66

20

66

40

66

60

Mn

1M

n2

Mn

3f"

_S

as

Energie (eV)

f" (électrons)

KK

Tra

nsf

orm

atio

n Energyshift off ’’

Energyshift off ’

_________________________________________________________________________



Conclusion o

n t

he

me

tho

dits

elf

�R

eso

na

nt

Diff

ract

ion

an

dD

AN

ES

is

po

ssib

le o

n p

ow

de

rs

Conclusion o

n t

heresonantcontribution r

efin

em

en

t�

diff

ere

nt

ed

ge

shift

s fo

r th

e3

Mn

site

s co

rre

spo

nd

ing

to3 valence states

ba

sed

on

stru

ctu

refa

cto

r se

lect

iviti

es

we

can

com

bin

e d

iffra

ctio

n a

nd

sp

ect

rosc

op

yin

form

atio

n


DAFS, DANES


FQ,E

()=

f iQ,E

()

i∑expiQ

.ri

()exp−BiQ

2(

)

Chemicalselectivity

Site selectivity

we

can

vary

the

con

trib

utio

n o

f o

ne

spe

cific

ato

mo

n d

iffra

cte

din

ten

sity


MAD


Contrast


_________________________________________________________________________



Lowlocal site symmetry

Pt2+

� ��Absorption issensitive

to directions of polarization

ex.

ofPlatinumPt2+

X-rayDichroïsm: AnisotropyofAnomalousScattering

� ��Anomalousscatteringtermsf' and f" varyfor different

directions of polarization

� ��tensorproperties*

* D

.H.

Te

mp

leto

n&

L.K

. T

em

ple

ton

, A

cta

Cry

st.

A4

1,

13

3 (

19

85

)

* A

. K

irfe

let

al.,

A

cta

Cry

st.

A4

7,1

80

(1

99

1);

A4

8,

24

7 (

19

92

); A

49

, 3

5 (

19

93

)*

V.E

.D

mitr

ien

koe

t a

l.,

Act

a C

ryst

. A

61

, 4

81

(2

00

5)

� ��Intensities

0 for forbiddenreflections(21, 41, .., n, c, d,..)

≠

� ��Diffractedintensitiesvarywithpolarizationdirection

and azimuthalangle *

_________________________________________________________________________



� ��on Powders: superposition ofreflectionsofdiffrentsgrains versus ψ ψψψ

ba

sed

on

stru

ctu

refa

cto

r se

lect

iviti

es

we

can

com

bin

e d

iffra

ctio

n a

nd

sp

ect

rosc

op

yin

form

atio

n


DAFS, DANES


FQ,E

()=

f iQ,E

()

i∑expiQ

.ri

()exp−BiQ

2(

)

Chemicalselectivity

Site selectivity

we

can

vary

the

con

trib

utio

n o

f o

ne

spe

cific

ato

mo

n d

iffra

cte

din

ten

sity


MAD


Contrast


_________________________________________________________________________



MMulti-wavelengthAAnomalousDDispersion

& SSingle AAnomalousDDispersion

� ��M

eth

od

s M

AD

& S

AD

use

d in

Biocrystallography

( ve

ry la

rge

ce

ll )

Structure factor phase solution (MAD & SAD methods)

FQ,E

()=

f iQ,E

()

i∑expiQ

.ri

()exp−BiQ

2(

)

F

F’

F” A

F

FN

Im

Re

A

F T

FA0

A

ΦA

∆Φ

∆Φ∆Φ

∆Φ= Φ

T-

ΦA

ΦT

FN

no

n a

no

ma

lou

sa

tom

s

FA

an

om

alo

us

ato

ms

∆Φ

∆Φ∆Φ

∆Φ= Φ

T-ΦA

� ��I(h, λ) = Abs.LP.λ3 .(IFTI2+(f

' A2 +

f"A2 )

IFA

I2/f

oA2 +2

IFTIIFA

I(f' Acos(∆Φ

∆Φ∆Φ

∆Φ)+

f"Asin(∆Φ

∆Φ∆Φ

∆Φ))/f

oA)

� ��Intensityvariation for thesamestructure

versus theenergyor for Friedel pairs

_________________________________________________________________________



� ��E

ffe

ct o

f a

no

ma

lou

s d

isp

ers

ion

on

diff

ract

ed

inte

nsi

ty o

f(hkl) and(-h-k-l)reflections

I+α

IFTI2 + ((fa’2+f a”2)/f oa2)IFAI2 + 2(fa’/f oa)IFTIIFAIcos(δΦ) +2(fa"/f oa)IFTIIFAIsin(δΦ)

I-α

IFTI2 + ((fa’2+f a”2)/f oa2)IFAI2 + 2(fa’/f oa)IFTIIFAIcos(δΦ) -2(fa"/f oa)IFTIIFAIsin(δΦ)

* K

arl

eJ.

In

t. J

of

Qu

an

tum

Ch

em

istr

y. 7

, 3

56

(19

91

)

** H

en

dri

ckso

n,

Sci

en

ce 2

54

, 5

1,

((1

99

1)

***

Pe

ters

on

et

al.

J. S

yn.

Ra

d.

3,

24

, (1

99

6)

�Bijvoetdifferences:

I +-I -proportional to f “and sin(δΦ)

�Dispersive differences:

I E1-I E2depends mainly on f ‘ E1-f ‘ E2

and cos(δΦ)

Bromine positions in a brominated

oligonucleotidecrystal as shown

by Patterson map ***

Structure factor phase solution and Contrast

_________________________________________________________________________



ba

sed

on

stru

ctu

refa

cto

r se

lect

iviti

es

we

can

com

bin

e d

iffra

ctio

n a

nd

sp

ect

rosc

op

yin

form

atio

n


DAFS, DANES


FQ,E

()=

f iQ,E

()

i∑expiQ

.ri

()exp−BiQ

2(

)

Chemicalselectivity

Site selectivity

we

can

vary

the

con

trib

utio

n o

f o

ne

spe

cific

ato

mo

n d

iffra

cte

din

ten

sity


MAD


Contrast


_________________________________________________________________________



� ��u

se t

hechemicalcontrast

to r

etr

ieve

thelocalisation ofa specificatom

Eff

ect

of

an

om

alo

us

dis

pe

rsio

n o

n a

diff

ract

ed

inte

nsi

ty :

I+α

IFTI2 + ((fa’2+f a”2)/f oa2)IFAI2 + 2(fa’/f oa)IFTIIFAIcos(δΦ) +2(fa"/f oa)IFTIIFAIsin(δΦ)

I-α

IFTI2 + ((fa’2+f a”2)/f oa2)IFAI2 + 2(fa’/f oa)IFTIIFAIcos(δΦ) -2(fa"/f oa)IFTIIFAIsin(δΦ)

� ��Bijvoetdifferences :

I +-I -proportional to f "

� ��Dispersivedifferences :proportional to f

’ λ1-f

’ λ2

But on powder diffraction:

�o

verl

ap

pin

g

of

I

+

an

d

I -

refle

ctio

ns

�h

ud

ge

ab

sorp

tion

eff

ect

� ��w

ea

k va

ria

tion

with

f "

h

ud

ge

fluo

resc

en

ce s

catt

eri

ng

on powder diffraction :

�th

e in

ten

sity

va

ria

tion

is s

ee

n

�w

ea

k a

bso

rptio

n is

po

ssib

le

� ��la

rge

r va

ria

tion

with

f ’

we

ake

r flu

ore

sce

nce

sca

tte

rin

g

ResonantContrastDiffraction : on powderdiffraction

_________________________________________________________________________



0

1 104

2 104

3 104

4 104

5 104

6 104

7 104

0,1

0,120,140,160,18

0,2

0,220,240,26

NaSrX EK(Sr)-900eV (-0.003Å-1 in 1/d shifted)

NaSrX EK(Sr)-65eV

NaSrX EK(Sr)-10eV (0.003Å-1 in 1/d shifted)

Intensities (u.a.)

1/d (Å-1)

(220)

(400)

(511) (333)

(422)

(311)

(331)

(533)

(222)

(440)

(620)

Resonant effects

on powder diffraction diagram

Va

ria

tion

s o

f (400)

an

d (331)

Bra

gg

ra

w in

ten

sity

d

iffe

ren

t w

ith e

ne

rgy

clo

sed

to

EK

(Sr)

.

Intensity variation for different energies (442)

ResonantContrastDiffraction : effecton Bragg intensities

_________________________________________________________________________



Variation of scattering due to resonantscatteringandf’(E)

Real scattering power (fo+ f') of Ni, Co, Mn

and Al as a function of q for energies far and

close to K edges of Ni, Co and Mnatoms

Jou

be

rt,

J.M

.; C

ern

y, R

.; L

atr

och

e,

M.;

Pe

rch

ero

n-G

ue

gu

an

, A

.; Y

von

. K

. J. Appl. Cryst.

19

98

, 31

, 3

27

Low 2θ θθθangle part of the observed and refined

diffraction patterns of LaNi3.55Mn0.4Al0.3Co0.75

for the same wavelengths or energies

_________________________________________________________________________



SrK absorption edge

ωω

ωω

ωπ

ωd

fP

f∫∞

−=

02 0

2

00

)(''

2)

('

ωω

ωω

πω

df

Pf

∫∞

−=

02 0

2

00

)('

2)

("

So

ftw

are

s: DiffKK

(Cro

ss,

J.O

.(1

99

8)

Ph

ys.

Re

v. B58

, 1

12

15

).

CHOOCH

(Eva

ns,

G.

& P

ett

ifer,

R.

(20

01

) J.

Ap

pl.

Cry

st. 34

, 8

2).

+ Introduction of a correction for white line

f’’(

E)

pro

po

rtio

na

lto

E.µ

(E)

f’Kramers-Kronigrelation�

f’’

Direct measurementoff’’

Accuratedeterminationoff’(E),f’’(E) on thesampleitself

_________________________________________________________________________



Po

res

Cation distributions determination :

Monocationic

zeolites

Bicationic

zeolites

Conventionaldiffraction

Resonantor anomalousdiffraction

performed with in situmeasurements

Strong evolution of cation distributions

with measurements conditions

Exa

mp

le in

de

hyd

ratio

n p

roce

ss:

No

rby,

P.,

Po

shn

i, F

.I.,

Gu

alti

eri

, A

.F.,

Ha

nso

n,

J.C

. a

nd

C

.P.

Gre

y(1

99

8) J. Phys. Chem. B102

, 8

39.

Adsorption selectivityin zeolitesdrivenby

cation distributions

SIII, SII, SI

_________________________________________________________________________



deshydratedSrX

hydratedSrX

(111) re

flection

Framework

atom

refine

ment

Extra-fram

emork

cation

refine

ment

ZeoliteSrX

XRD powderpatterns ofhydrated& deshydratedzeolites

_________________________________________________________________________



()

()

()

{}

∑⋅

−=

H

rH

Hr

iF

Vπ

ρ2

exp

1

Electron density(ρ ρρρ)in a chanelplane ofSrX-D

Cation distribution visualizedin direc

t sp

ace

ρ ρρρ obs-ρ ρρρcalc

0,126

0,1

11

0,0

96

0,0

81

0,0

65

0,0

50

0,0

35

0,0

20

0,0

04

-0,0

11

-0,0

26

-0.0

42

-0,0

57

-0,0

72

-0,0

87

-0,103

19,039

17

,89

31

6,7

46

15

,60

01

4,4

53

13

,30

61

2,1

60

11

,01

39

,86

78

,72

07

,57

46

,42

75

,28

04

,13

42

,98

71

,84

10

,69

4-0,453

ρ ρρρ obs

×( I diff= 1

,2 %

I ob

s(m

ax)

)

_________________________________________________________________________



CaSr

X de

shyd

raté

27

88.0

62

26

24.0

58

24

60.0

54

22

96.0

51

21

32.0

47

19

68.0

44

18

04.0

40

16

40.0

36

14

76.0

33

13

12.0

29

11

48.0

25

9

84.0

22

8

20.0

18

6

56.0

15

4

92.0

11

3

28.0

07

1

64.0

04

O1

O1

O1

O1

O1

O1

O1

O1

O1

O1

SI

SI’

SII

SII’

SrRbX multi-pattern refinement 209-3

41

47.3

78

39

16.9

68

36

86.5

58

34

56.1

48

32

25.7

38

29

95.3

28

27

64.9

18

25

34.5

09

23

04.0

99

20

73.6

89

18

43.2

79

16

12.8

69

13

82.4

59

11

52.0

49

9

21.6

40

6

91.2

30

4

60.8

20

O1

O1

O1

O1

O1

O1

O1

O1

O1

O1

SI

SI’

SII

SII’

in bicationiczeolites:

-two cationsmay occupy the same site,

-Improvement of resolution does not always lead to

cationcontribution separation

Re

solu

tion

: 0

.88

Å

Sr 25Rb16X

r Sr2

+=

1.1

8Å

r Rb

+ =

1.5

2Å

Sr 22Ca18X

r Sr2

+=

1.1

8Å

r Ca

2+

=1

.00

Å


t sp

ace

Electron density(ρ ρρρ)in a chanelplane

Need of a selective probe : Resonant Diffraction

Rb+= 36 e-

Sr2+= 36 e-

_________________________________________________________________________



H. Palancher, C. Pichon, B. Rebours, J. Lynch,

-10-8-6-4-20246 16000

16040

16080

16120

16160

16200

f'_ca

lculé

f"_me

suré

f'_Cr

omer

-Libe

rman

f"_Cr

omer-

Liber

man

EK(Sr)

f’ (e-)f"(e-)

Energy(eV)

f’ andf“variations close to absorption edgeEK(Sr)for cation Srin SrRbX

�se

nsi

tivity

to

ch

em

ica

lsta

tea

nd

en

viro

nm

en

t

�measurement of the

absorption on the

sample itself

�determine f’ by using

KramersKronigrelation

Rb+= 36e- , Sr2+= 36e-

EK(S

r)-9

00

eVf’ = -2.55 e-

EK(S

r)-6

5e

Vf’ = -4.94 e-

EK(S

r)-1

0e

Vf’ = -6.79 e-

EK(Sr)-10eV

EK(Sr)-65eV

+ EK(Sr)-900eV

�o

ptim

iza

tion

of

the

en

erg

ies

Energyselection& determinationoff’(E),f’’(E) on powder

_________________________________________________________________________



-2.0E+04

0.0E+00

2.0E+04

4.0E+04

6.0E+04

8.0E+04

1.0E+05

1.2E+05

1.4E+05

010

20

30

40

50

60

2*θ θθθ(°)

Intensities (a.u.)

Measured Intensity

Calculated Intensity

Difference between calculated

and measured intensities

-4.00E+03

-2.00E+03

0.00E+00

2.00E+03

46

810

12

14

2*θ θθθ (°)

Difference between calculated and measured intensities

(220)

(311)

(222)

(400)

(422)

(442)

(440)

(333) or (511)

(620)

(533)

(444)

(331)

(531)

(622)

Far from the edges, good fit butno chemical discrimination between Sr2+and Rb+

0.0E+00

1.0E+04

2.0E+04

3.0E+04

46

810

12

14

Measured Intensity

Calculated Intensity

I x

5

I x

10

Cation distribution visualizedin rec

ipro

calsp

ace

SrRbX-H

_________________________________________________________________________



Visualization in rec

ipro

cal sp

aceof resonant effects near

the edge via“anomalous differential pattern”

-4.00E+03

-2.00E+03

0.00E+00

2.00E+03

46

810

12

14

2*θ θθθ (°)

Difference between calculated and measured intensities

(220)

(311)

(222)

(400)

(422)

(442)

(440)

(333) or (511)

(620)

(533)

(444)

(331)

(531)

(622)

0.0E+00

1.0E+04

2.0E+04

3.0E+04

46

810

12

14

Measured Intensity

Calculated Intensity SrRbX-H

atSr

K e

dg

e

-4.00E+03

-2.00E+03

0.00E+00

2.00E+03

0.1

0.14

0.18

0.22

0.26

I(EkSr-10eV)-I(EkSr-1300eV)_measured

(220)

(311)

(222)

(400)

(422)

(442)

(440)

(333) or (511)

(620)

(533)

(444)

(331)

(531)

(622)

atRb

K e

dg

e

-4.00E+03

-2.00E+03

0.00E+00

2.00E+03

0.1

0.14

0.18

0.22

0.26

I(EkRb-10eV)-I(EkRb-400eV)_measured

(220)

(311)

(222)

(400)

(422)

(442)

(440)

(333) or (511)

(620)

(533)

(444)

(331)

(531)

(622)

Close to the edges: cation discrimination

Significant anomalous signal even in powders

I x

5

I x

10

_________________________________________________________________________



Sr 25Rb16X

SrRbX 237-1

SIII

SI

SII

SI’

SII’

SI’

SII SII’

SI’

SI

SI’

O4

O4

O2

O3

O2

O2

O2

O3

O2

O3


t sp

ace

X or Y zeolite structure

()

()

()

{}

∑⋅

−=

H

rH

Hr

iF

Vπ

ρ2

exp

1

Electron density (ρ ρρρ)maps calculated by Fourier transform

Localisation ofcations withclose Z

Rb

+=

36

e- ,

Sr2

+=

36

e-

_________________________________________________________________________



H.

Pa

lan

che

re

t a

l. A

ng

ew

. C

he

m.

Int.

Ed

. (2

00

5)

44

, 1

1,

17

25

.

Diff

ere

nce

be

twe

en

an

om

alo

us

da

ta a

nd

ca

lcu

late

d o

ne

with

∆f

’= 0

Visualization in direc

t sp

aceof resonant effects

near the edge via“dispersive difference maps”

in situcharacterisationofcationicdistributions in bicationicSrRbX-Hzeolite

Z(S

r2+)

= Z

(Rb

1+)

= 3

6e

-

Rb+cation location and quantification

SrX multi-pattern refinement

04

04

02

03

02

03

SII

SI

03

03

02

02

SI

SII’

SII

SI’

SII’ SI’


04

04

02

03

02

03

SII

SI

03

03

02

02

SI

SII’

SII

SI’

SII’ SI’

atRb

K a

bso

rptio

n e

dg

e

1,088

1,0

12

0,9

36

0,8

61

0,7

85

0,7

09

0,6

33

0,5

58

0,4

82

0,4

06

0,3

30

0,2

55

0,1

79

0,1

03

0,0

28

-0,0

48

-0,124

nE

ffEanomal

−∆

ρ ρρρ obs

Sr2+cation location and quantification

atSr

K a

bso

rptio

n e

dg

e

1,327

1,2

42

1,1

57

1,0

72

0,9

87

0,9

03

0,8

18

0,7

33

0,6

48

0,5

63

0,4

78

0,3

93

0,3

08

0,2

23

0,1

38

0,0

53

-0,0

32

-0,1

16

-0,2

01

-0,286

nE

ffEanomal

−∆

ρ ρρρ obs


04

04

02

03

02

03

SII

SI

03

03

02

02

SI

SII’

SII

SI’

SII’ SI’


04

04

02

03

02

03

SII

SI

03

03

02

02

SI

SII’

SII

SI’

SII’ SI’

Sr 25Rb16X

SrRbX 237-1

SIII

SI

SII

SI’

SII’

SI’

SII SII’

SI’

SI

SI’

O4

O4

O2

O3

O2

O2

O2

O3

O2

O3

H.

Pa

lan

che

re

t a

l. A

ng

ew

. C

he

m.

Int.

Ed

. (2

00

5)

44

, 1

1,

17

25

._________________________________________________________________________



Difference between anomalous data and calculated one with true ∆f

’

Visualization in direc

t sp

aceof resonant effects

near the edge via“dispersive difference maps”

in situcharacterisationofcationicdistributions in bicationicSrRbX-Hzeolite

resi

du

ala

tSr

K a

bso

rptio

n e

dg

ere

sid

ua

latRb

K a

bso

rptio

n e

dg

e

∆f

’(Sr)

= -4,6 e-

∆f

’(Rb

) =

-4,3 e-

0,232

0,2

06

0,1

80

0,1

54

0,1

28

0,1

03

0,0

77

0,0

51

0,0

25

-0,0

01

-0,0

27

-0,0

52

-0,0

78

-0,1

04

-0,1

30

-0,1

56

-0,182

0,163

0,1

49

0,1

35

0,1

21

0,1

08

0,0

94

0,0

80

0,0

66

0,0

53

0,0

39

0,0

25

0,0

11

-0,0

03

-0,0

16

-0,0

30

-0,0

44

-0,0

58

-0,0

71

-0,0

85

-0,099

nE

ffEanomal

−∆

(ρ ρρρobs-ρ ρρρ calc

)nE

ffEanomal

−∆

(ρ ρρρobs-ρ ρρρ calc

)

no residuals !

H.

Pa

lan

che

re

t a

l. A

ng

ew

. C

he

m.

Int.

Ed

. (2

00

5)

44

, 1

1,

17

25

._________________________________________________________________________



Evaluation in reciprocal space,of the quality of determined structural model

Ag

ree

me

nt

in in

ten

sity

be

twe

en

ca

lcu

late

d a

nd

me

asu

red

re

son

an

t d

iffe

ren

tial p

att

ern

s Im

ple

me

nta

tion

of

this

ca

lcu

latio

n in

th

e F

ullP

rof

soft

wa

reatRb

ab

sorp

tion

ed

ge

-4.00E+03

-2.00E+03

0.00E+00

2.00E+03

0.1

0.14

0.18

0.22

0.26

1/d (A-1)

I(EkRb-10eV)-I(EkRb-400eV)_measured

I(EkRb-10eV)-I(EkRb-400eV)_calculated

(220)

(311)

(222)

(400)

(422)

(442)

(440)

(333) ou (511)

(620)(533)

(444)

(331)

(531)

(622)

-4.00E+03

-2.00E+03

0.00E+00

2.00E+03

0.1

0.14

0.18

0.22

0.26

1/d (A-1)

I(EkSr-10eV)-I(EkSr-1300eV)_measured

I(EkSr-10eV)-I(EkSr-1300eV)_calculated

(220)

(311)

(222)

(400)

(422)

(442)

(440)

(333) or (511)

(620)

(533)

(444)

(331)

(531)

(622)

atSr

ab

sorp

tion

ed

ge

Visualization in rec

ipro

cal sp

aceof resonant effects near

the edge via“anomalous differential pattern”

SrRbX-H

_________________________________________________________________________



H.

Pa

lan

che

re

t a

l. A

ng

ew

. C

he

m.

Int.

Ed

. (2

00

5)

44

, 1

1,

17

25

.

Crystallographic

cationsites

H2O

H2O

H2O

H2O

H2O

Site I

Site I’

Site II

Site II’

supercage

25

10 5 015

20

Number of cations per unit cell

Sr2+

Rb+

Importance of contrast measurements for direct atom

localization for in-situstudies

II’

II’

III

II

II

H2O

p-C8H10

p-C8H10

p-C8H10

p-C8H10

p-C8H10

C C

C C

CC

/ Xylene

_________________________________________________________________________



4N

a1

+

13.8 ±0.9

Rb1+

Sr2+

29.5 ±2.5

Resonant diffraction on

dehydrated SrRbX

Cation

amount

(per unit cell)

Chemical composition of SrRbX:

80.8

78.7

Ne

ga

tive

ch

arg

es

of

the

fra

me

wo

rk

(ele

me

nta

ry a

na

lysi

s)P

osi

tive

ch

arg

es

(An

om

alo

us

diff

ract

ion

)Electric

chargesEfficiencyofResonantContrastDiffraction

for atomlocalization

II’

II’

III

II

II

Resonant Contrast Diffraction on powders :

good efficiency via the use of

-“anomalous differential patterns”,

-“dispersive difference maps”

_________________________________________________________________________



Study of mixed phaseswith different crystallinity

,

� ��Differential

anomalous pattern

�differentiate interzeolite

and intrazeoliteparticles

�localizationoffccmetallicPt

ZMS-5 zeolites(3 wt% Pt)

_________________________________________________________________________



Thanksto H. Palancher, ChPichon, J. Lynch, B. Rebours, S. Bos, E. Lorenzo, J.F. Berar

ResonantDiffraction isan

extremelyselectiveprobe for :

� ��atomiclocal environment

� ��nano systems

� ��modulatedstructure

� ��Distortionstudies

� ��Charge Orderingstudies

� ��Structure determination

� ��Atomlocalizationin complexsystems

we

can

com

bin

e d

iffra

ctio

n a

nd

sp

ect

rosc

op

yin

form

atio

n

� ��SelectiveSite Spectroscopy: DAFS & DANES

DAFS & DANES


we

can

vary

the

con

trib

utio

n o

f o

ne

spe

cific

ato

mo

n d

iffra

cte

din

ten

sity


MAD


Contrast


_________________________________________________________________________


LLB-SOLEIL march 2006 hodeau@_grenoble.cnrs.fr

Documents

ction ours, Resonant Diffraction on Powders -Site