To derive Bragg ' s law :;
1. We consider a series of parallel planes
of the same Miller ' s indices (The atomic density ,
the number of atoms intersecting by each plane / unit area would be same )
2. For example , we are considering the planes with (h, k, l) = (1, 1, 1)
3. θ here is the diffraction angle
→ →
4. k and k' are the momentum of the incident and diffracted X - rays, respectively
5.
2 d Sin θ = m λ is obtained using the Laue ' s condition
→ → →
k' - k = G
2 [Link]
111 plane
→ →
Think of the condition ⅇ ⅈ G .T = 1
→ →
Clearly G is ⟂ to the Miller plane . Say G0 is the smallest vector in that direction
Also a plane of constant phase , is chracterised by
→ →
G.r = constant
and one of such plane is
→ →
G0 .r = constant
If you move from one plane to the next (WITHIN THE SAME MILLER FAMILY ),
you have moved a distance
d along the normal direction and the phase change is
→ → → → →
→
→
Δϕ = G0 .r + dn - G0 .r = G0 .dn = G0 . dn = G0 d
Two adjacent planes in a crystal are identical , so the phase change must be exactly
2 π (one full wave cycle ) :
→
G0 d = 2π
→ →
Now think of the vector G when you go about m number of planes from G0
→ 2π →
G = m=m G0
d
Structure factor (Concept of single crystal diffraction along with the Bragg law )
[Link] 3
→ → →
ⅈ →
∝ n ⅇ
2 G -Δk .r
I= FD → → d3 r 2
Volume of the sample G G
Let ' s consider
→ →
G - Δk = 0
3 → →
I∝ n d r
→ →
2
∝ → n →
2
d3 r 2
Volume of the sample G G G G Volume of the unit cell
I∝ → n →
2
V2
G G
→
→
→
A reminder n r = n ⅇ ⅈ G .r → →
G G
2
It means that if we have an idea about n → ,
G
we can always predict the diffraction pattern .
2
How do we find n → ?
G
→
→
→
Let ' s write the inverse Fourier transform of n r = n ⅇ ⅈ G .r → →
G G
1 →
→ →
n → = n r ⅇ -ⅈ G .r d3 r
G hkl
Vcell V cell
→
→
→
The integral n r ⅇ -ⅈ G .r d3 r
V cell
is the scattering density of one unit cell called as structure factor , denoted by Shkl .
→
You need to know n r within the cell. For example , in case of BCC,
1 1 1 →
I have an atom at (0, 0, 0) and , , . This information is enough for n r.
2 2 2
α is the position of the atom.
4 [Link]
→ 1 1 1
for a BCC, rα = (0, 0, 0) and , ,
2 2 2
→
r would be any point in the unit cell.
→
rα would be the position vector of the atom.
→
r ' would point from the atom to any point in the unit cell.
→
If you want to know the full information about n r,
we have to consider each atom in the unit cell
→ → →
n r = → n r - rα
rα
→
→
→
Shkl = n r ⅇ -ⅈ G hkl .r d3 r
V cell
→
→ →
→
Shkl = → n r - rα ⅇ -ⅈ G hkl .r d3 r
V cell rα
to add the contribution from all the atoms in the unit cell
→ → →
r - rα = r '
→ → →
→ G hkl . r α + r ' → →
Shkl = nα r ' ⅇ d3 rα + r '
-ⅈ
→
V cell rα
→ → →
→ G hkl . r α + r ' →
Shkl = nα r ' ⅇ
-ⅈ
→ d3 r '
V cell rα
→ →
→ →
→ →
Shkl = ⅇ nα r ' ⅇ -ⅈ G hkl .r ' d3 r '
-ⅈ G hkl .r α
→
rα V cell
→
→ →
→
The quantity nα r ' ⅇ -ⅈ G hkl .r ' d3 r ' is called the atomic form factor , fα
V cell
→ →
The quantity ⅇ -ⅈ G hkl .r defines the atomic location in a cell
α
I∝ Shkl 2
[Link] 5
Example : CsCl crystal (has a BCC lattice )
α = Cs, Cl
rCs (0, 0, 0) (They are not hkl )
1 1 1
rCl , ,
2 2 2
The atomic form factor is fixed for a given atom, fCs for Cs atom and fCl for Cl atom
→ → → → → →
Shkl = ⅇ -ⅈ G hkl .r fα = ⅇ -ⅈ G hkl .r Cs fCs + ⅇ -ⅈ G hkl .r Cl fCl
α
→ → → →
G = h g1 + k g2 + l g3
→ → → → → →
-ⅈ g 1 + k g2 + l g3 . a3
1 1 1
Shkl = fCs + ⅇ
a1 + a2 +
2 2 2
fCl
ai .gj = 2 π δ ij
Shkl = fCs + ⅇ -ⅈ π h + k + l fCl
-1 h + k + l = odd integer
ⅇ
-ⅈ π h + k + l
=
1 h + k + l = even integer
fCs + fCl h + k + l = even integer
Shkl = fCs + ⅇ -ⅈ π h + k + l fCl =
fCs - fCl h + k + l = odd integer
The diffraction intensity is as below
6 [Link]
Note : All planes are contributing to the diffraction intensity .
The indication in green colors denotes the plane (100 ) (110 )
(111 ) (200 ) (210 ) (211 ) (220 ) (221 ) (300 ) (310 ) (311 ) .... from left ro right
Suppose we have Cs in place of Cl,
2 fCs h + k + l = even integer
Shkl = fCs + ⅇ -ⅈ h + k + l fCs =
0 h + k + l = odd integer
The diffraction pattern is given below
The indication in green colors denotes the plane (100 ) (110 )
(111 ) (200 ) (210 ) (211 ) (220 ) (221 ) (300 ) (310 ) (311 ) .... from left ro right
See it yourself , whether they follow the
2 fCs h + k + l = even integer
Shkl = fCs + ⅇ -ⅈ h + k + l fCs =
0 h + k + l = odd integer
[Link] 7
Shkl is important in determining which plane
will contribute to the intensity at the detector .
HW : Find the Structure factor for an FCC lattice .
→ →
→ →
→ →
Shkl = ⅇ -ⅈ G hkl .r α
nα r ' ⅇ -ⅈ G hkl .r ' d3 r '
α
V cell
An FCC lattice has 4 lattice sites per unit cell.
(From which number to which number )
α
This summation will run from 1 to 4
where the second ,
third and fourth atoms / lattice sites are the nearest neighbours to the first atom.
8 [Link]
→
1 st rα = (0, 0, 0)
→ 1 1
2 nd rα = 0, ,
2 2
→ 1 1
3 rd rα = , 0,
2 2
→ 1 1
4 th rα = , ,0
2 2
This term
→
→ →
→
nα r ' ⅇ -ⅈ G hkl .r ' d3 r ' would be the same for all atoms since they are all alike .
V cell
→
→ →
→
fFe = nα r ' ⅇ -ⅈ G hkl .r ' d3 r '
V cell
→ →
Shkl = ⅇ -ⅈ G hkl .r fFe = α
α
→ → → → → → → → → → → → → → → → → →
-ⅈ g 1 + k g2 + l g3 .0 a1 + a3 -ⅈ g 1 + k g2 + l g3 . a3 -ⅈ g 1 + k g2 + l g3 . a2 + 0 a3
1 1 1 1 1 1
fFe 1 + ⅇ +ⅇ +ⅇ
a2 + a1 + 0 a2 + a1 +
2 2 2 2 2 2
→ →
Shkl = ⅇ -ⅈ G hkl .r fFe = fFe 1 + ⅇ -ⅈ π k + l + ⅇ -ⅈ π h + l + ⅇ -ⅈ π h + k
α
1 m = even
From Euler relation , ⅇ -ⅈ π m =
-1 m = odd
4 fFe when all the h, k, l are either even / odd
Shkl = fFe 1 + ⅇ -ⅈ π k + l + ⅇ -ⅈ π h + l + ⅇ -ⅈ π h + k =
0 When there odd and even h, k, l are mixed
→ → → →
Ghkl = g1 + k g2 + l g3
→ →
gi .aj = 2 π δ ij
h = 2;
k = 2;
l = - 2;
fFe 1 + ⅇ -ⅈ π k + l + ⅇ -ⅈ π h + l + ⅇ -ⅈ π h + k
4 fFe
[Link] 9
10 [Link]
Given a lattice structure → predict the diffraction intensity →
We confirm the type of lattice from the diffraction intensity
It helps you to identify the lattice struture .
Why to do the diffraction expt when you already know the position of atoms in a crystal ?
In reality , you are given a sample ,
Guess the structure of the sample , predict the intensity ,
compare the intensity with the experimental finding (which contains only I and θ),
if they don ' t agree , you make another quess and if
they do you can conclude that the quess structure was correct .