Crystal Structure Determination

A Crystal behaves as a 3-D

Diffraction Grating for X-Rays
• In a diffraction experiment, the spacing of lines on the grating
can be found from the separation of the diffraction maxima.
Also, information about the structure of the lines on the
grating can be obtained by measuring the relative
intensities of different orders
• Similarly, measurement of the separation of the X-Ray
diffraction maxima from a crystal enables the
determination of the unit cell size. Also, from the
intensities of diffracted beams, information can be
obtained about the arrangement of atoms within the cell.
 X-Ray Crystallography
• For X-Rays, the wavelength λ is
typically  a few Ångstroms,
which is comparable to the
interatomic spacing (distances
between atoms or ions) in crystals.
• So, for crystal structure
determination, the X-Rays have
to be of energy:

hc hc
Exray    h    12.3x10 eV
3

 1x10 m
10
 Bragg Law
• Consider crystals as made up of parallel planes of atoms.
Incident waves are reflected specularly from parallel planes
of atoms in the crystal, with each plane reflecting only a
very small fraction of the radiation, like a lightly silvered mirror.
• In mirrorlike reflection, the angle of incidence is equal to
the angle of reflection.

ө ө
 Diffraction Condition
• The diffracted beams are found to have maximum intensity when the


Reflections from Planes of Atoms
Interfere Constructively.
Assume elastic scattering, in which the X-Ray energy isn’t changed on reflection.
• So, when X-Rays strike a crystal, we want the condition for constructive
interference between reflected rays from different planes. That is, we want the
condition for the reflected X-rays to be in-phase with one another so
that they that add together constructively.

Incident
 angle
Reflected
 angle
Wavelength
 of X-rays
 2


Total Diffracted
Angle  2
 Bragg Law
• The two X-Ray beams travel different distances. The difference in the
distances traveled is related to the distance between the adjacent layers.
• See figure. Connecting the two beams with perpendicular lines shows the
difference in the distance traveled between top & bottom beams.
• In the figure, the length DE is the same as EF, so the total distance traveled by
the bottom wave is expressed by: DE  EF  2d sin 
• Constructive interference of the radiation from successive planes
occurs when the path difference is an integral number of wavelengths.
This is called the Bragg Law n  2d sin 
DE  d sin 
EF  d sin 
NOTE:
Line CE = d = distance
between the 2 layers
 Bragg Law
(Bragg Equation)
2d sin   n
d = Spacing of the Planes, n = Order of Diffraction.

2d sin  n
• Because sin θ ≤ 1, Bragg reflection can only occur for
wavelengths satisfying:
n  2d
• This is why visible light can’t be used. No diffraction
occurs when the above condition is not satisfied.
• The diffracted beams (reflections) from any set of lattice
planes can only occur at particular angles predicted by
Bragg’s Law.
 A similar, but slightly different viewpoint:
Scattering of X-Rays from Adjacent
Lattice Points A & B


• Consider X-Rays incident at angle θ on one of the planes of the set.
• There will be constructive interference of the waves
scattered from the two successive lattice points A & B in
the plane if the distances AC and DB are equal.

D C

  2
A B
Constructive Interference
of Waves Scattered from the Same Plane
• If the scattered wave makes the same angle with the
plane as the incident wave

The diffracted wave will look as if it was reflected from the plane.
• It is common to consider scattering from lattice points
rather than atoms because it is the basis of atoms associated
with each lattice point that is the true repeat unit of the crystal.
• The lattice point is an analogue of the line on an optical
diffraction grating & the basis represents the structure of the line.
 Diffraction Maximum
• Coherent scattering from a single plane is not sufficient

2d sin  n
to obtain a diffraction maximum. It is also necessary
that successive planes also scatter in phase.

• This will be the case if the path difference for scattering

of two adjacent planes is an integral number of
wavelengths

2d sin   n
 Additional Notes on Bragg Reflections
• Although the reflection from each plane is specular, only
for certain values of  will the reflections from all planes
add up in phase to give a strong reflected beam.
• Each plane reflects only 10-3 to 10-5 of the incident
radiation, i.e. it is not a perfect reflector. So, 103 to 105
planes contribute to the formation of the Bragg-reflected
beam in a perfect crystal.
• The composition of the basis determines the relative
intensity of the various orders of diffraction.
 Scattered Wave Amplitude 
Reciprocal Lattice Vectors
• Now, consider X-Ray Scattering from crystals & analyze the

Amplitude of the Scattered Waves.

• The electronic number density n(r) in the crystal is a periodic
function in space: n(r) = n(r +T)
with period T equal to a Direct Lattice Translation Vector,
T = n 1 a1 + n 2 a2 + n 3 a3
• So, n(r) can be expressed as a Fourier series expansion.
• For a one-dimensional model crystal, n(x) can be represented as

 
n( x)  n0   C p cos(2px / a )  S p sin(2px / a )   n p ei 2px / a
p 0 p
where the p’s are integers and a
n p  1a  dxn( x)e i 2px / a
0
In 3 dimensions, this has the form:
a
iG r
n(r )   nG e  nG  V  dVn(r )e iGr
1
(1)
G c
0

The vectors G are called Reciprocal Lattice Vectors

As we said, the electronic density n(r) is required to be invariant
(periodic) under lattice iG r iG T n(r) = n(r +T)
iG (r  T)translations: iG T (2)
n(r  T)   nG e   nG e e  n(r ) when e 1
G G (3)

Only the set of Reciprocal Lattice Vectors G that satisfy both (1) & (3)
lead to an n(r) invariant under lattice translations. It’s not too hard to show
that the set ofGReciprocal
 v1b1  v2bLattice
2  v3b 3Vectors G that meet this requirement are
of the form
a j where
 a k υ1, υ2 and υ3 are integers and the bi’s
The a areare
’s defined
the as:
primitive lattice
b i  2 , i  x, y, z  bi  a j  2ij
 
j
ai  a j  a k
vectors for the crystal structure.

It also can be shown that the set of

Reciprocal Lattice Vectors G is a Bravais Lattice!
Diffraction Condition (Bragg’s Law)
in the Reciprocal Lattice
An X-Ray diffraction pattern of the lattice can be interpreted as a
map of the reciprocal lattice of the crystal. The above statement is
consistent with the following theorem:
The set of Reciprocal Lattice Vectors G
determines the possible X-ray
r reflections.
The scattering wave amplitude
d w
{

is given by:
{

k F   dVn(r )ei (k k')r

  dVn(r )e ik r
k´ When G = k (wavevector),
then F = V nG.
 Now look at this condition for the case of elastic scattering:
G  k  k'k  2k  G  G 2  0
This result is called The Laue Condition.
It’s not too difficult to show that it is 100% equivalent to
The Bragg Law!
The result that k = G can also be expressed to give the relations that
are called The Laue Relations or the Laue Equations. These are
obtained by taking the dot product of both Δk & G with a1, a2 & a3:
k  ai  2vi , i  1,2,3
The Laue Equations
G
By changing θ, X-Ray diffraction can
 k´ 2θ
be used to map all Reciprocal
k Lattice Vectors. This geometric method
of finding Reciprocal Lattice Vectors is
called the Ewald Construction
 Brillouin Zones & Reciprocal Lattices
for the SC, BCC & FCC Lattices
Brillouin Zones
The First Brillouin Zone (BZ) is defined as the Wigner-Seitz
primitive cell in the reciprocal lattice. It gives a geometric
interpretation, in the reciprocal lattice, of the diffraction condition.

• The Brillouin construction exhibits

all wavevectors k that can be
Bragg reflected by the crystal.
• The constructions divide the
reciprocal space into fragments,
out of which the First Brillouin
Zone is of the greatest importance.
 Reciprocal Lattices for the SC, FCC & BCC Lattices
Direct Lattice Reciprocal Lattice
Volume
 a1  ax  b1  2 / a x
  2 / a 3
SC a 2  ay b 2  2 / a y
 a  az  b  2 / a z
 3  3
 a1  1 ax  y  b1  2  x  y  z 
2  a
 2  x  y  z 
a 2  2 ay  z 
1 
b
 2 a 22 / a 3
FCC a  1 az  x  b  2 x  y  z 
 3 2  3 a
a1  1 ax  y  z   b1  2 y  z 
2  a

a 2  2 a x  y  z 
1  2  x  z 
BCC b
 2 a 42 / a 3
a  1 ax  y  z  b  2 x  y 
 3 2  3 a
Brillouin Zones: Square Lattice
First 4 Brillouin Zones: Square Lattice
All Brillouin Zones: Square Lattice
First Brillouin Zone: BCC Lattice
First Brillouin Zone: FCC Lattice
Reciprocal Lattice for Aluminium
 Fourier Analysis of a Basis
Structure Factor & Atomic Form Factor.
Recall that the scattering amplitude is:

F   dVn(r)e iG r  NSG

cell
The quantity SG is called The Structure Factor. It is defined as an
integral over a single unit cell. If the electron density is written as a
superposition of the electron densities in the cell, taking into account
the # of atoms in the basis, it has the form:
s
n(r )   n j (r  r j )
j 1
where s is the # of atoms in the unit cell.
 Using this, The Structure Factor has the form:
s
SG    dVn j (r  r j )e iGr
j 1 cell
s iG r j s iG r j
iG 
 e  dVn j ()e  e fj
j 1 cell j 1
The quantity fj is called The Atomic Form Factor. Now specifying
G and rj as
G  v1b1  v2b 2  v3b3 and r j  x j a1  y j a 2  z j a3
s  2 i x j v1  y j v2  z j v3 
gives: SG   f j e
j 1

Note that SG can be complex, because the scattering

intensity involves the magnitude squared of SG.
• If the electron density of the atom is spherically-
symmetric, the atomic form factor fj can be written:
2 sin Gr 

f j  4  n j ( r ) r dr
0 Gr

This means that when the electronic density has the form
n(r) = Zg(r), then fj = CZ
(C = constant, Z = atomic charge,)
That is, in this case, fj is the ratio of radiation amplitude
scattered by the electron distribution to that scattered by
a localized electron.
 Examples of Structure Factor Calculations
BCC lattice
For a BCC lattice, there are two atoms per unit cell
located at (000) & (½½ ½). The structure factor is then:


SG  1  e  i v1  v2  v3 
f
The structure factor is maximum SG = 2f when the sum
of the indices is even, i.e.
υ1+ υ2+ υ3= 2n (n = integer)

The structure factor SG = 0 when the sum of the indices is odd, i.e.
υ1+ υ2+ υ3= 2n + 1 (n = integer)
Examples of Structure Factor Calculations
FCC lattice
For a FCC lattice, there 4 atoms per unit cell located at
(000), (0½½), (½ 0½) & (½½0). So, the structure factor is:

 
SG  1  e  i v1  v2   e  i v1  v3   e  i v2  v3  f
When all indices are even or odd, then SG = 4f.
When the indices are partially even & partially odd, then SG = 0.

To summarize, in a FCC lattice, no reflections occur

when the indices are partially even and partially odd.
Observed & Calculated
Atomic Form Factor for Aluminium
 From Ch. 1:
Lattice Planes & Miller Indices
• A Lattice Plane is any plane containing at least three
non-colinear Bravais lattice points.
• Generally, a lattice plane is described by giving a
vector normal to that plane, and there happens to be
reciprocal lattice vectors normal to any lattice plane.
• Choose the the shortest such reciprocal lattice vector
to arrive at the Miller indices of the plane.
• Thus a plane with Miller indices h, k, l, is normal to
the reciprocal lattice vector hb1 + hb2 + hb3.
 From Ch. 1:
Lattice Planes & Miller Indices, Continued
Review of Miller Indices
Imagine representing a crystal structure on a grid (lattice) which is a
3D array of points (lattice points). Now, imagine dividing the grid
into sets of “planes” in different orientations:
Review of Miller Indices, continued
Recall that
• All planes in a set are identical.
• The perpendicular distance between pairs of adjacent planes
is the d-spacing.
• Miller Indices define the orientation of the plane within the
unit cell.
• The Miller Indices define a set of planes parallel to one
another.
(002) planes are parallel to (001) planes, and so on
• So, in analyzing crystal diffraction results, the lattice planes are
labeled with their Miller Indices (hkl) for their identification.
 Labelling the Reflection Planes
• Label reflections with the Miller indices of the planes.
• A beam corresponding to a diffraction order of n >1
could be identified by a statement such as
“the nth-order reflections from the (hkl) planes”
or a (nh nk nl) reflection”.

Example
A 3rd order reflection from the (111) plane is
“a (333) reflection”
 nth Order Diffraction Off of (hkl) Planes
• Rewriting the Bragg Law:
d 
2  sin   
 n
which makes nth order diffraction off of (hkl)
planes of spacing “d” look like 1st order
diffraction off planes of spacing (d/n).

• Planes of this reduced spacing would have Miller

indices (nh nk nl).
 X-Ray Structure Analysis of NaCl & KCl
General Prıncıples of X-Ray Structure Analysıs
Applied to Find the Crystal


Structures of NaCl & KCl
• The Braggs measured the intensity of specular reflection
from cleaved faces of NaCl & KCl crystals.
• They found 6 values of θ for which a sharp peak in intensity
occurred, corresponding to 3 characteristic wavelengths (K,L and M
X-Rays) in 1st & 2nd order (n = 1 and n = 2 in the Bragg Law)
• By repeating the experiment with a different crystal face they
could use the Bragg Equation to find, for example, the ratio of
(100) & (111) plane spacings, information that confirmed the cubic
symmetry of the atomic arrangement.
 Details of the Structure
• Details of the crystal structure were then found. They also
discovered some surprising differences between the diffraction
patterns for NaCl and KCl.
A Major Difference
was the absence of (111) reflections in KCl compared to weak but
detectable (111) reflections in NaCl.
• The explanation for this is that the K and Cl ions both have the argon
electron shell structure and hence scatter x-rays almost equally.
However, the Na and Cl ions have very different scattering strengths.
The (111) reflection in NaCl corresponds to a one wavelength path
difference between neighboring (111) planes.
 Measurement Results

XRD Pattern
for NaCl

XRD Pattern
for KCl
 d - Spacing Formula
d ≡ Distance between Parallel Lattice Planes
with Miller Indices (hkl)
Its not difficult to prove the following:
Orthogonal Cubic
Crystal Systems Crystal
( =  =  = 90) Systems
(a 2= b =2c)
1 h 2
k l 2 2
1 h k l 2

2
 2 2 2 2

d a b c d a2
(special case of orthogonal systems)
 Bragg Equation
• Since Bragg's Law applies to all sets of crystal planes, the lattice
structure can be found from the diffraction pattern, making use of
general expressions for the spacing of the planes in terms of
their Miller indices (hkl), along with the Bragg Law.
• For cubic structures
a
d 2d sin   n
h k l
2 2 2

Note that the smaller the spacing, the higher the angle
of diffraction, i.e. the spacing of peaks in the diffraction pattern
is inversely proportional to the spacing of the planes in the lattice.
The diffraction pattern will reflect the symmetry properties of the lattice.
Some Results for d-2 for Some Non-Cubic Lattices
 Bragg Equation
• A simple example is the difference between the
series of (n00) reflections for a simple cubic and
a body centred cubic lattice. For the simple cubic
lattice, all values of n will give Bragg peaks.
• However, for the body centered cubic lattice the (100)
planes are interleaved by an equivalent set at the
halfway position. At the angle where Bragg's Law
would give the (100) reflection the interleaved planes
will give a reflection exactly out of phase with that
from the primary planes, which will exactly cancel
the signal. So, in the BCC lattice, there is no
signal from (n00) planes with odd values of n.
This kind of argument leads to rules for identifying
the lattice symmetry from "missing" reflections,
which are often quite simple.
Another (Equivalent) Treatment
of The Reciprocal Lattice
• From another internet source. Slightly different notation, sorry!
• Suppose we have a Bravias Lattice, with translational
vector R, & a plane wave, eik·r. Generally, for a given k, the
plane wave will not have the periodicity of the Bravais
lattice, R. However, for a given R, there will be a set of
wave vectors, K, that will yield plane waves with the
periodicity of the Bravais lattice.

eiK·r = eiK·(r + R) = eiK·r eiK·R

thus,
eiK·R = 1 or K·R = 2nπ
 The Reciprocal Lattice
• The Reciprocal lattice is a Bravais lattice. A brief proof:

bi = 2π(aj × ak )/(ai • aj × ak) then bi • aj = 2 π δij.

Furthermore, any vector, k, can be written as
k = k1b1 + k2b2 + k3b3.
For any vector in the direct lattice, R,
k • R = 2 π(k1n1 + k2n2 + k2n2 ),
so for eik • R to be unity for all R, k • R must be 2π times an
integer n. So the coefficients ki must also be integers.
Therefore, the set of Reciprocal Lattice Vectors,
K are themselves a Bravais lattice
 The Reciprocal Lattice:
Some other comments.
• The reciprocal lattice of the reciprocal lattice?
– Is just the direct lattice!
• Brillouin Zone
– Brillouin zones are primitive cells that arise in the
theories of electronic levels - Band Theory and
lattice vibrations - phonons.
– The first Brillouin zone is the Wigner-Seitz
primitive cell of the reciprocal lattice.
 Another (Equivalent) Treatment
Von Laue Formulation of Crystal Diffraction
• From another internet source. Slightly different notation, sorry!
• Doesn’t assume specular reflection
• No sectioning by planes
• Rather, at each point on the Bravais lattice the incident ray is
allowed to be scattered in all directions
 First, consider only two scatterers.

k = kn

θ k´ = kn´
d
θ´
The path difference is then
d cosθ + d cosθ´ = d • (n - n´),
k = 2πn/λ The condition for constructive
k´ = 2πn´/λ interference is,
d • (n - n´) = mλ
• With an array of scatterers; one at each point of the
Bravais lattice
• The results on the last slide must hold for each d that are
Bravais lattice vectors, so
R • (k - k´) = 2πm
(m = integer) or
eiR • (k - k´) = 1!!!!
Compare this to the definition for the reciprocal lattice!
This is just The Laue Condition:
Constructive interference will occur provided that
the change in wave vector,
K = k´ - k, is a vector in
the reciprocal lattice.
 Ewald Construction
The condition for constructive interference is that
K = k´ - k, is a vector of the reciprocal lattice.

Doing this for all k & k´ generates the Reciprocal Lattice