OUTLINE

SOME INTRO ONELECTROMAGNETIC WAVES

THOMSON SCATTERING

SCATTERING FACTOR
ONE DIMENSION CRYSTAL : INTERFERENCE FUNCTION AND STRUCTURE FACTOR

3D CRYSTALS , LAUE EQUATIONS , BRAGG LAW

PROPERTIES OF STRUCTURE FACTORS

HOW TO SOLVE A CRYSTAL STRUCTURE

 Electromagnetic waves
• Equation de propagation

E =E0 exp i( wt –k.r +φ) s0

• Periode, pulsation , frequence
• T =2π/w
• Longueur d’onde vecteur d onde
k=2 π / λ
 X Ray-Matter Interactions
I scatt
Thomson and Compton scattering

MATTER
I0 Xray incoming beam θ IT Transmitted beam

Due to absorbtion

Compton Scattering Inelastic incoherent scattering Energy transferred from X rays to the
electrons Momentum Density : electron density in momentum space

Thomson Scattering Elastic coherent scattering

Electron density in direct space
 Compton scattering
- Diffusion Compton
La diffusion Compton est une diffusion incohérente inélastique des rayons X caractérisée par
un changement de longueur : une partie de l’énergie X est transférée a la cible et le faisceau
transmis voit donc sa longueur d’onde augmenter. Analyser la diffusion Compton permets de
modéliser la densité électronique dans l’espace des impulsions ( quantités de mouvement) .
On obtient la distribution de la densité de quantité de mouvement dans l’espace .
 I THOMSON SCATTERING : FREE ELECTRON
a. Linearly Polarized Electromagnetic wave

Détecteur
→
E →
→
→ s K
so 
→
→ e R
Ko

As Thomson scattering is → re → →
Ee ( R ) = - Eo R sin  exp i (t - K . R )
proportional to the inverse 
of the mass of the charged
re2
particules, most scattering Ie = Io 2 sin2 
comes from the electron ; R
the nuclear scattering is 10-3
e2
weaker in amplitude re = electron classical radius =2.818 * 10 – 5 Angstroem
4omc2
therefore 10-6
in intensity
→ 2 → → 2 →  
Ko = s o; K = s ; s = so =1
 
An Xray diffraction experiment will mostly give the electron density

b. Perfectly non polarized electromagnetic wave

2
re 1 + cos2 2
Ie = Io 2  
R  2 

re 1 + cos2 21/2 → →
Ee = Eo R 

 exp i ( t - K. R)
 2 

Ee complex amplitude of the scattered electric field by a free electron


 X RAY SCATTERING BY A COLLECTION OF FREE ELECTRONS P
Detecteur
a.Two electrons (at O and A)

Détecteur

H A
A
→ r
E
→
→ →
RR
r
S
s
K
Ko
0
So S 2θ
The two scattered beams interfere at long distance ( detector) O
H
S0

s
S
D =AH +AK = r.- s0 + r.s
2 = r. ( s- s0)
0
Ssoo
Δ φ = 2πD /λ = 2π r. ( s- s0) /λ
→ →
→ s - so → 2 sin 
H= ; H =
 
H= ( s- s0) /λ
→→
E = Ee (1 + e2i H . r )
 
Δ φ= 2π H.r
b. N point sources

→→ →→ →→
E = Ee [1 + exp (2i H . r 1) + exp (2i H . r 2) + ... exp (2i H . r n-1)]
 

N-1
= Ee
  exp (2 →H .→r j) Fonction d interference
j=0

E(H) = Ee[1 + exp (2i H.r1) + exp (2i H.r2 ) + + exp (2i H.r3 ) + ... exp (2i H.rn-1 )]

Ee σ𝑁
0 exp (2i H.rj )

Fonction d interference
 II SCATTERING BY AN ATOM : CONTINUOUS CHARGE DENSITY :
SCATTERING (FORM) FACTOR

dq elementary charge inside the scattering atom at r ; dE is is elementary

field scattered by dq
d E = Ee dq exp(2πiH.r)= Ee 𝜌(r)exp(2πiH.r ) dV
  
Scattering factors normalized at 1 e-
Valence
1.2
1
0.8
Electrons

0.6
0.4
0.2
0 Sin θ/λ ,Å-1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
-0.2

1.2 Core
1

0.8
Electrons

C
0.6 N
O
0.4 S
P
0.2 Br
F
0 Sin θ/λ , Å-1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
f is the scattering factor ( or form factor ) of the free independent atom , it is the
Fourier transform of the electron density
 Anomalous scattering
The Thomson scattering is valid for a free electron only
As the electrons are tight to the nuclei and respond less than a free atom to
the X ray electric field the scattering factor is reduced by f’ ( f’ negative ) .
Furthermore if the wavelength is close to the absorption edge of the scattering
atom the absorption coefficient increases and photoelectric effect occurs
Then f is a complex number

f= f0 +f’ ( λ ) +I f” ( λ )
n =no – δ + iβ

f’ and f “ are therefore function of the wavelength ( energy) and of the

nature of the scattering atom .
Application to contrast :

Supposse we have an Fe Ni alloy to study ; they have mostly the same electron
densityand therefore a very close scattering factor ; working close to Fe or Ni
absorption edge will enhance the f” component of Fe ( or Ni) and therefore
allow to distinguish these 2 elements
STRUCTURE FACTOR
In any volume of matter, crystalline or not, each atom j scatters the
Xray photons and therefore the scattered electric field is:
Na
→ →→
E( H ) = E e
   fj(H) exp(2πi H . r j)
j=1
  

Scattering by scattering phase shift

the free electron factor function of the rj atomic position

Na is the total number of atoms in the scattering sample which is huge

The most important quantity is therefore the structure factor Na
→ →→
F( H ) =  fj exp2πi H . r j
j=1
Application: Debye Formula
The Debye formula can be applied to a gaz , liquid , solid or nanomaterial
It gives the scattered intensity of the sample when exposed to Xrays ( or
neutrons)

Where Nat is the total number of atoms in the sample , rjk is the the distance between atom j
and atom k and Tj the average thermal motion of atom j . This formula relates therefore the
scattered intensity to the interatomic distances . Due to the huge number of atoms in the
sample such a formula is difficult to apply ; it is however used now for solving the structure
of nanomaterials .
 III ONE DIMENSION CRYSTAL : THE INTERFERENCE FUNCTION
(→
H)

O rj
• ∆ □ ○ • ∆ □ ○ • ∆ □ ○ • ∆ □ ○ • ∆ □ ○
rjn
→ →
r jn = (xj + n) a for ’atom j of unit cell n :
xj fractional coordinate of atom j

N-1 nat N-1 nat

→ →→ → →
E( H ) = Ee   fj exp(2πi H . r jn) = E
   e   fj exp2πi H .(xj + n) a
n=0 j=1 n=0 j=1

1 + e 
         
nat 2 iH.x j a 2 iH.a 2 iH.2a 2 iH.na 2 iH.( N −1) a
= Ee  fj e +e + e + e
 j

 nat → → → → →
E(H)

= Ee   fj e2πi H .xj a  ( H )
 = Ee F( H ) ( H )
j=1  

→ → → → → →
I( H ) is proportional to E( H )* E( H ) =Ee2 ( H ) =Ee F2( H ) ( H )
  
CONCLUSION

→  nat 2πi→ →
F( H ) = 
 j f e H .x j a ; it only depends on the coordinates of the atoms
j=1 
of the unit cell (nat) ; it contains therefore the necessary information for crystal
structure solution

→ →
( H ) is the interference function directly linked to the lattice parameter ( a ),

and to the number of unit cells (N), it does not depends on the content of the

unit cell; it characterizes the geometry of the scattering experiment ie the

→ →
→ → s - so → 2 sin 
position of vector H H= ; H = therefore
 

the respective positions of the incoming and diffracted beams

→
( H ) is a geometric sum ; it can be shown that the scattered intensity is :

→ r
2
1 + cos 2 2 →
I( H )= Io e 2 ( sin2( NπH.a) / sin2( πH.a)) F2( H )
R 2

→
Where the yellow part of the equation is ( H )
If N is small ( nanocristal for example ),the interference function has intense
maxima equal to the square of the number of unit cells ( N2) and secondary
maximas which intensity decreases with the number of unit cells . Such a
scattered figure is called diffraction . The intense maxima are for directions
where the beams scattered by all unit cells are in phase, therefore for :
→→
2 H . a = 2 h
→→
ie H . a = h with h positive, zero or negative integer

When the number N of unit cell is large the secondary maxima are very weak
and cannot be measured .The interference function is therefore the sum of Dirac
→→
functions which peak at H . a = integers

N2
 DEFINITION OF THE RECIPROCAL LATTICE OF A ONE DIMENSIONAL
CRYSTAL

→→ → →
H . a = (projection of the H vector on the lattice parameter a )* a = h

→ →
(Projection of H vector on the lattice parameter a )= h/a

→
Therefore the extremity of H vector belongs to a infinite serie of parallel planes
→
equally spaced by 1/a and perpendicular to the lattice parameter a .

The planes are called the reciprocal lattice of the one dimensional crystal
Reseau reciproque a deux dimensions
 GENERALISATION TO A 3 DIMENSIONAL LATTICE
If we perform the same calculation for a 3D crystal which has Na unit cells in
direction a, Nb unit cells indirection b, Nc unit cells in direction c ,
ie N= Na *Nb*Nc unit cells , any atomic vector of the crystal is written as

Rj na nb nc =rj+na a +nb b +nc c

The intensity of the diffracted beam is

I(H) = Ie F2(H) 2(H)

→→ →→ →→
→ sin2 (Na H . a ) sin2 (Nb H . b ) sin2 (Nc H . c )
with 2 ( H ) =
→→ →→ →→
sin2 ( H . a ) sin2 ( H . b ) sin2 ( H . c )

If N is large we have diffracted beams only if the next 3 equations are satisfied
together:
→→
H. a = h 
→→
H. b = k 
Laue equations ( 1912) , Nobel prize in 1914
→→
H. c =  
These Laue equations are equivalent to
 
→ s − s → → →
H= = ha*+kb*+c*

With h,k, l coordinates of the H reciprocal lattice vector
The reciprocal lattice H vectors have therefore their extremity at the
intersections of the three one dimensional lattice planes defined by the three
Laue equations; this definition of the reciprocal lattice is equivalent to

ai * aj = δij or a* = V (→
b →
1
c)
if the direct lattice are in angstroms Å the reciprocal lattice parameters are in Å-1
EWALD SPHERE
THIS CONCEPT OF EWALD SPHERE OF RADIUS (1/) ,CENTRED ON THE DIFFRACTING
CRYSTAL, IS VERY USEFUL FOR INTERPRETATION OF THE DIFFRACTION EXPERIMENTS
We recall the two definitions of H

 
→ s − s → → →
H= = ha*+kb*+c*

 
→ s s
H+
 =
BRAGG LAW

2 sin  1
│H│= =
 d(h,k,)

==> 2d sin  = 
incomin diffractd
g

→
s/

  H
(h,k,l) plane
d(h,k,l) 

so/
 FORBIDDEN EXTINCTIONS AND SPACE GROUP DETERMINATION

Lattice Mode ( P, I, A ( B, C),F)

Example : Lattice mode I

x, y, z → x + 1/2, y + 1/2, z +1/2

Nat
==> F(h, k, ) =  fj exp(2i(hxj+kyj+zj))
j=1

Nat/2
=  fj exp(2i(hxj+kyj+zj)) (1 + exp(i (h+k+))
j=1

Therefore all reflections with :

(h + k + ) = 2n + 1 have zero intensity

 Glide planes

→
Example : c orthorhombic crystal : c glide plane perpendicular to b (x0z)

x, y, z → x, –y , z + 1/2

Nat/2
F(h, 0, ) =  fj exp(2i(hxj+zj)) (1 + exp i)
j=1

extinction for the reciprocal mirror (h, 0, ) with  = 2n + 1.

 Most important extinctions are shown below

Lattice Mode Reflections Extinctions

A h, k,  k +  = 2n +1
B h, k,  h +  = 2n +1
C h, k,  h + k = 2n +1
I h, k,  h + k +  = 2n +1
F h, k,  h, k,  different parity
Glide planes
0yz 0, k, 
b k = 2n + 1
c  = 2n + 1
n k +  = 2n + 1

x0z h, 0, 
a h = 2n + 1
c  = 2n + 1
n h +  = 2n + 1

xy0 h, k, 0
a h = 2n + 1
b k = 2n + 1
n h + k = 2n + 1
21 axix
x00 h, 0, 0 h = 2n + 1
0y0 0, k, 0 k = 2n + 1
00z 0, 0,   = 2n + 1
 HOW TO DETERMINE A SPACE GROUP?

We have to look to the symmetry and extinctions of the diffracted beams

- Unit cell parameters a, b, c, , , , mass density ;

- Point group of the diffraction pattern and hypothesis concerning the

point group of the diffracting

- Systematic extinctions and space group

EXERCICE
- The relations between diffracted intensities are :

– – – –
I (h, k, ) = I (h, k, ) = I (h, k , ) = I (h, k , )

Which point groups verify these relations ?

- the systematic extinctions are:

 h, k,  h + k +  = 2n + 1
On the planes 0k k = 2n + 1
h0 h = 2n + 1
hk0 no extinction
 RELATIONS BETWEEN STRUCTURE FACTOR AND ÉLECTRON
DENSITY

→
j( r ) of atom j is linked to the scattering factor by Fourier transform
→  →  → → →
j( r ) =  fj ( H ) exp -2 H . r  d3 H

The electron density of the Unit cell is the inverse Fourier transform of the structure
factors
→  →  → → →
( r ) =  F( H ) exp -2i H . r  d3 H
Vmaille*

→
F( H ) is discrete ( non zero only at reciprocal lattice points ) then

→
( r ) = V
-1
 F(→H ) exp -2i→H .→r  V is the unit cell volume
→
H
→ → →
F( H ) = │F( H )│exp i φ( H )
→
phase φ( H )is not given by experiment;

for each point (x,y,z) of the unit cell on can calculate :

(x, y, z) = V-1    F(h, k, ) exp [ -2i (hx + ky + z)]

h k 
This sum goes over on all measured F(H) ; therefore one has the problem of Fourier
truncation errors :if I((h, k, ) are measured to (sin max) / , one says that the
experimental resolution is:
s = sin max /  (Å-1)

or in direct space d = (Å)
2sin max
 THERMAL DISPLACEMENT PARAMETERS
→
An atom at T vibrate around its average position r o
→ → →
r = ro + u
Then the dynamic structure factor at time t is :
Nat Nat
→
F( H )=  fk (→H ) exp 2i→H .→r k=  fk (→H ) exp 2i→H .→r ok exp 2i→H .→u k
k=1 k=1

→ → → →
The contribution to F( H ) of u k is a function of the projection of u k on H
Using a diffractometer , measuring a Bragg reflection is very long compared
the atomic vibrations period (10-15 s), which are large compared the period of
the incoming X beam (10-18 s) ; therefore each photon sees an atom at rest and
we observe an average of the phase shift :

→
F( H )=  fk exp 2i→H .→r ok < exp 2i→H .→u k > =  fk exp 2i→H .→r ok WTk(H)
k k
WTk is the Debye Waller factor of atom k at temperature T.
The Debye Waller factor is :

Isotropic motion of atom k

 2 sin2  2   sin2
Wk(H) = exp - 82 < uk >  = exp -22 < u > H2 = exp - Bk 
 2   k   2 

Bk is the isotropic displacement parameter of atome k ; Bk = 8 π2 <u2k>.

Anisotropic motion (Uij)

W(H) = exp [-22 (h2U11a*2 + k2U22b*2 + 2U23c*2 + 2hkU12a*b* + 2

hU13a*c* + 2kU23b*c*)]

avec Uij = < ui uj >, i, j = 1,3 coefficients of the U tensor of anisotropic

displacement. They are represented by an ellipsoid

The thermal vibrations in fact decrease the coherence between diffracted waves
therefore the diffracted intensity .
c. Interprétation

For harmonic motion , the probability density of the atom is a gaussian

P(u) = [det U-1]1/2 / 23/2] exp -[T u U-1 u]
 

With U = < u Tu > atomic displacement tensor (U11 = < u12 >, U12 = < u1 u2
  
>...)

therefore the constant probability surface are defined by the quadratic form :

T n U-1 n = cste
 
 Molecular crystal

Ellipsoids of TTF Ca
Crystal Structure determination
R X diffraction summary

H= ha* +kb* + lc* H
dhkl = 1/ H
X-ray ,n , é

2dhkl sin =  dhkl

Plans ( h,k,l) du cristal


 I(H ) = K* 2 * F2
 Interference function F Structure Factor

( ) ( )
Fourier transform of the lattice  Na  
F H =  f j H exp(2iH .r )
j =1
ai . aj* = ij Fourier transform of the electron
density of the unit cell
Sources de rayonnement

Tube a rayons X

Synchrotron voir film

Neutron
 Sources de laboratoire
Tubes à rayons X
principe:
E(X) filament (W)
h= ~ 10-6 Z V(kV) < 1%
E(e-)
e-
Pmax = 2 kW X

anticathode (Cu, Fe, Mo, Ag)

tube de Coolidge (1913)

Sources de laboratoire
Anode tournante
Microsources
Rayonnement caracteristique
 Mécanisme de production des rayons X
« de laboratoire »

rayonnement blanc + raies caractéristiques

K
L

rayonnement de freinage effet photoélectrique

Bremstrahlung
 Sources de laboratoire
Paramètres des sources de laboratoire
(Å)

K1 K2 K
✓ intensité i du courant
intensité
Cr 2.294 2.290 2.085
✓ haute tension V
K Fe 1.940 1.936 1.757
✓ matériau cible Co 1.793 1.789 1.621
Cu 1.544 1.540 1.392
K Mo 0.7135 0.7093 0.6323
Pmax 30 kV
Ag 0.5638 0.5594 0.4970
IK ~ i (V – VK) ~
n (V – VK)1.63
V
20 kV

V 10 kV
~ 2.5 - 3
VK 0.5 1.0 1.5 2.0 2.5 3.0 3.5
longueur d’onde (Å)
ex.: Mo (2kW) VK = 20 kV, i = 40 mA, V = 40 kV
Rayonnement synchrotron

http://dl.free.fr/nBhS1tHPW
 Synchrotron: la machine

anneau de
2,75 GeV
stockage
booster
110 MeV

linac

ligne de
Soleil lumière
Chambre à vide
P ~10-10 mbars
 Une lumière naturellement pulsée

Ex. Soleil
Mode uniforme : 416 paquets : 1 impulsion ~ 14 ps toutes les ~ 3 ns
en réalité, ¾ rempli (312 paquets)

« Structure temporelle » :8 paquets : ~30 ps toutes les ~ 150 ns

Ex. ESRF
992 paquets : ~20 ps

24x8 + 1 paquets : ~25 ps

16 paquets : ~48 ps

4 paquets : ~55 ps
 Onduleur / Wiggler

u

s’z
gap s’x

amplitude d’oscillation K ~ u [cm] B0 [T] gap, i

K >> 1 wiggler K 1
I ~ 2N I(wiggle) s’x ~  s’z ~ 

1
K~1 onduleur I ~ N2 I(wiggle) s’x ~ s’z ~
N
 Synchrotron (SR) versus conventional sources

Advantage of the SR

. high flux which high order data collection on weakly

diffracting crystals,
. parallel beam which reduces peak width therefore
TDS integration
. possibility to choose low wavelengths (0.4 Å or less)
which reduces absorption and extinction.
.A data collection may be performed in few hours
which may be interesting for instable crystals.

The problem with SR is unstability

source de RX Paramètres caractéristiques du
nombre de photons émis source:

source échantillon

ph/s
Flux : D
ph/s/mrad/ =0.1% (1 mrad ~ 0.06°)


Luminosité: ph/s/mrad2/0.1%BW (Brigthness)

Brillance: ph/s/mrad2/mm2/0.1%BW
Brillance des sources
 III NEUTRON SCATTERING
Mass mn =1.675 .10-27kg Similar to proton mass
Life time = 887s
Charge 0 Magnetic moment =- 1.913 μn Spin = ½

The neutron is higtly penetrating and non

destructive
Sensitive to magnetic structure and magnetic
fluctuations
The spin can be polarized
It has particle and wave properties
λ= 9.04 𝑬 in meV
1 meV = 11.61K= 8.07 cm-1

Energy ( meV) Temp (K) Lambda (Ǻ)

Cold 0.1 – 10 1 – 120 30 - 4
Thermal 5 – 100 60 -1000 4- 1
Hot 100- 500 1000- 6000 1 – 0.04

Boltzman distribution of energies

 Neutron scattering
Scattering by a nucleus :
The energy of n is too small to perturb the
nucleus elastic process

The nuclear force has a range of a Fermi, therefore the

neutron sees the nucleus as a point

And the nuclear scattering length b is independent of the

theta angle
Element H D U Fe Co Ba O V Ti Zr
X-ray f (0°)
1 1 92 26 27 56 8 23 22 40
(Z)
Neutron b - - -
6.674 8.420 9.450 2.780 5.280 5.805 5.280
(fm) 3.740 0.3824 3.438

A direct comparison can be made by multiplying f (0°) value by the

classical electron radius, re, equal to 2.818 fm.
Note that "heavy" elements do not scatter on average very much more
than lighter ones
 Neutron scattering

b is a constant versus sin/ (angular resolution) .

b is isotope dependant
its value does not follow the periodic table
contrary to the Xrays scattering factor f (sin/) .
 Utmost property of the neutron
diffraction the Magnetic form factor
magn. UC

FM(H) = j=1
bMj(H)exp[2i(H·rj)]·Tj(H)

bMj(H) = (e2/2mec2)fMj(H)sm⊥j(H)
• neutron spin operator ½ s
• m⊥j(H) is the projection of the
magnetic moment mj onto the scattering plane (hkl)
magnetic form factor fMj(H):
Fourier transform of the normalised
magnetization density Mj(r)
of the atom j

fMj(H) = V Mj(r)·exp[2i(H·r)]·dr
The intensity of a magnetic Bragg reflection depends
on the relative orientations of magnetic moment mj and
scattering vector H = [hkl]*
Comment collecter nos données de
diffraction?
Diffractomettre Kappa
Kappa in X8APEX

© 2001 Bruker Nonius BV. All Rights Reserved

Detecteur a pixels monté sur un diffractomètre Bruker-
Nonius MACH3 :prototype du CRM2
1)Collect the Xray data ie the maximum of bragg reflections in all
directions of space at a given T with a single crystal diffractometer
 Comment fonctionne le difffractometre ?

rotation du cristal (typiquement par pas de 1°) et

collecte simultanée des intensités diffractées
 Images de diffraction: monocristal

Cristal non orienté / RX Cristal non orienté / RX

« pas » du réseau 3D

Propriétés géométriques du diffractogramme

→ Connaissance de la structure périodique de l’objet diffractant
Ici le « pas » du réseau 3D = géométrie et symétrie de la maille élémentaire
Mesure des intensités diffractées (par intégration des pics)
→ Connaissance du motif = contenu (atomique ou moléculaire) du cristal
 Analyse du diagramme de diffraction

Des dizaines voire centaines d’images

Donc des milliers de spots de diffraction
Plus de 100 000 si cristal de protéine

L’intensité d’un spot ( pic de Bragg)

dépend de la densité électronique du plan
qui diffracte ( loi de Bragg)

Donc de la position des atomes dans ce plan

on verra dans ce cours comment calculer les

Espace réciproque du cristal Cartes de densité électronique dont les

Maxima correspondent a la position des atomes

 - EXPERIMENTAL REQUIREMENTS FOR CRYSTAL
STRUCTURE DETERMINATION

  
 
  
I meas ( H ) = k I Bragg ( H ) A( H ) 1 +  ( H ) y ( H ) +  p m I Bragg ( H m ) + I bkg
−2

Absorption TDS Extinction

o
3 2
e 
I Bragg  I  r (v / V )(1 / sin 2 ) (1 + cos 2 ) / 2 Fo 2
 2
1) Data reduction: correct for systematic errors and get the structure factor
amplitudes

Indexation des pics de Bragg

Integration
Corrections
Moyenne des reflections equivalents
Calcul du module de F (h,k,l) et de sa variance
Fichier de F(H), Sigma ( H)
 Intensity corrections

- Absorption

I corr = I o exp( − t )

Crystal faces indexing

A = V −1  exp−  (t o + t d )dv
Vcrystal
Moyenne des reflexions equivalentes
Calcul des variances sur les intensités mesurées

Determine the space group using systematic extinctions

Use direct methods heavy atom method for estimating the structure
factors phases

Calculate first electron density maps and assign the maxima's to the
atoms of the asymmetric unit

Crystal structure hypothesis and calculation the R statistic indexes

based on I or F

wR2(F) = [Σw [ Fobs - k |Fcal| ]2 / Σw Fobs2 ]1/2

S = [ Σw [Fobs-|Fcal|]2 / (n-p) ]1/2
R(F) = Σ[Fobs- k Fcal ] / ΣFobs;

n is the number of reflections number of reflections , and p is the total number

of parameters refined
Diffraction par une poudre

.
2d sin  = 

cones de diffraction

RX monochr.

capillaire

Detecteur 2D
Imaging plate
CCD
Detector pixels
DIFFRACTION PAR UN ECHANTILLON POLYCRISTALLIN

Diffractogramme de poudre :
2 d sin  =  Extraction du diagramme {yi(2 )}

yi

Analyse des intensités: Grand nombre de cristallites d’orientation aléatoire

Intensités relatives constantes sur des cônes d angle 2 theta
A chaque plan cristallin correspond un angle de diffraction donc un cône
d angle  suivant la loi de Bragg 2 d sin  = 
 Exemple de diffractogramme de poudre
Alun KAl(SO4)2,12H2O

Carte d identité de l alun

 Optiques pour les Rayons X
Miroirs (focalisants)

Rayons X n = 1 –  + i n <
~ 1 réflexion totale pour  < c

 
’
 > c n  < c

1  r 2 c = 2 c ~ mrad
 = 0  ~ 10-5


réflexion totale + courbure du miroir (courbure idéale = ellispe)

q q
~ p
focalisation p
~  q  = erreur de pente (rad)
 Exemples de systemes basse T

Cryostat realisé au laboratoire Soufflette Oxford Cryosystems

New cryostat built in LCM3B 3<T<100 K

CCD détector
Mini gonoimeter
Slave Magnet

Master Magnet

T minimale 4K d>35 mm
P. Fertey et col. Axis j
J. Appl. Cryst. (2007). Axe 
 Friedel Law and Laue Groups

No Anomalous dispersion
I(H)= I(-H)
Donc le module de F(H ) est égal au module de F( -H)
Et la phase α(H ) est egale à - α(-H )
A diffraction est donc un phenomene centrosymetrique ( principe du
retour inverse de la lumiere)
11 Groupes de Laue ( groupes centrosymètriques

Si diffuseur anomal f= f0 +f’ + if ’’ alors on peut distinguer un groupe

centro d un groupe non centro