Diffraction Conditions

Bragg angle  = ;  +  = 90; sin = sin = cos

𝐤 ∙ 𝐫 = 𝐤𝐫 𝐬𝐢𝐧 𝛟 = 𝐤𝐫 𝐬𝐢𝐧 𝛗 = 𝐤𝐫 𝐬𝐢𝐧 𝛉

r sin r
 Phase factor
= exp 𝑖 𝐤 − 𝐤 ′ ∙ 𝐫

1
 Theorem. The set of reciprocal lattice vectors 𝐺 determines the
possible x-ray reflections.

We see in Fig. 6 that the difference in phase factors is expሾ𝑖 𝐤 − 𝐤 ′ ∙

𝐫ሿ between beams scattered from volume elements 𝐫 apart.
The wavevectors of the incoming and outgoing beams are 𝐤 and 𝐤 ′ . We
suppose that the amplitude of the wave scattered from a volume element is
proportional to the local electron concentration 𝑛 𝒓 .
The total amplitude of the scattered wave in the direction of 𝐤 ′ is
proportional to the integral over the crystal of 𝑛 𝒓 𝑑𝑉 times the phase factor
exp 𝑖 𝐤 − 𝐤 ′ ∙ 𝐫 .

2
The amplitude of the electric or magnetic field vectors in scattered
electromagnetic wave is proportional to the following integral which
defines the quantity 𝐹 that we call the scattering amplitude:

𝐹 = න 𝑑𝑉 𝑛 𝐫 exp 𝑖 𝐤 − 𝐤 ′ ∙ 𝐫 = න 𝑑𝑉 𝑛 𝐫 exp −𝑖∆𝐤 ∙ 𝐫 (18)

where 𝐤 − 𝐤 ′ = −∆𝐤, or
𝐤 + ∆𝐤 = 𝐤 ′ (19)
Here ∆𝐤 measures the change in wavevector and is called the scattering
vector (Fig. 7).
We add ∆𝐤 to 𝐤 to obtain 𝐤 ′ , the wavevector of the scattered beam.
3
Figure 7 Definition of the
scattering vector ∆𝐤 such that
𝐤 + ∆𝐤 = 𝐤 ′ . In elastic scattering
the magnitudes satisfy 𝑘 ′ = 𝑘.
Further, in Bragg scattering from
a periodic lattice, any allowed ∆𝐤
must equal some reciprocal
lattice vector 𝐆.

4
 We introduce into (18) the Fourier components (9) of 𝑛 𝐫 to obtain
for the scattering amplitude

𝐹 = න 𝑑𝑉 𝑛𝐆 exp 𝑖 𝐆 − ∆𝐤 ∙ 𝐫 (20)
𝐆
When the scattering vector ∆𝐤 is equal to a particular reciprocal
lattice vector,
and 𝐹 is ~ 0 when ∆𝑘 ≠ 𝐺 ∆𝐤 = 𝐆 (21)
the argument of the exponential vanishes and 𝐹 = 𝑉𝑛𝐺 .

5
In elastic scattering of a photon its energy ℏ𝛚 is conserved, so that the
frequency 𝜔′ = 𝑐𝑘 ′ of the emergent beam is equal to the frequency of
the incident beam.
′ 2 ′2
Thus the magnitudes 𝑘 and 𝑘 are equal, and 𝑘 = 𝑘 , a result that
holds also for elastic scattering of electron and neutron beams.
From (21) we found ∆𝐤 = 𝐆 or
𝐤 + 𝐆 = 𝐤′,

So that the diffraction condition is written as 𝐤 + 𝐆 2 = 𝑘 2 , or

2𝐤 ∙ 𝐆 + G𝟐 = 0 (22)

6
 This is the central result of the theory of elastic scattering of
waves in a periodic lattice.
𝟐𝐤 ∙ 𝐆 = G𝟐 (23)

This particular expression is often used as the condition for diffraction.

Equation (23) is another statement of the Bragg condition (1).
The result of Problem 1 is that the spacing 𝑑 ℎ𝑘𝑙 between parallel
lattice planes that are normal to the direction 𝐆 = ℎ𝐛1 + 𝑘𝐛2 + 𝑙𝐛3 is
𝑑 ℎ𝑘𝑙 = 2𝜋Τ 𝐆 . Thus the result 𝟐𝐤 ∙ 𝑮 = 𝐺 2 may be written as
2 2𝜋Τ𝜆 sin 𝜃 = 2𝜋Τ𝑑 ℎ𝑘𝑙 , 𝐆 = 2πΤdhkl
or 2𝑑 ℎ𝑘𝑙 sin 𝜃 = 𝜆. Here 𝜃 is the angle between the incident beam
and the crystal plane.
7
 The integers ℎ𝑘𝑙 that define 𝐆 are not necessarily identical with
the indices of an actual crystal plane, because the ℎ𝑘𝑙 may contain a
common factor 𝑛, whereas in the definition of the indices in Chapter 1
the common factor has been eliminated. We thus obtain the Bragg
result:
(24)
The Bragg’s Law 2𝑑 sin 𝜃 = 𝑛𝜆,
where 𝑑 is the spacing between adjacent parallel planes with indices
ℎΤ𝑛, 𝑘 Τ𝑛, 𝑖 Τ𝑛.

8
 Laue Equations

∆𝐤 = 𝐆
𝑎1 ∙ ∆𝐤 = 2𝜋𝜐1
(25)
𝑎2 ∙ ∆𝐤 = 2𝜋𝜐2
𝑎3 ∙ ∆𝐤 = 2𝜋𝜐3
➢ ∆𝐤 must satisfy all three equations; it must lie at the common line of
intersection of three cones, which is a severe condition that can be
satisfied only by systematic sweeping or searching in wavelength or
crystal orientation—or by sheer accident.

9
Ewald Sphere Construction
Figure 8 The points on the right-hand side
are reciprocal-lattice points of the crystal.
Reciprocal lattice The vector 𝐤 is drawn in the direction of
the incident x-ray beam, and the origin is
chosen such that 𝐤 terminates at any
reciprocal lattice point. We draw a sphere
of radius k = 2𝜋Τ𝜆 about the origin of 𝐤.
A diffracted beam will be formed if this
sphere intersects any other point in the
reciprocal lattice. The sphere as drawn
intercepts a point connected with the end
of 𝐤 by a reciprocal lattice vector G. The
diffracted x-ray beam is in the direction
𝐤 ′ = 𝐤 + 𝐆. The angle is the Bragg angle
of Fig. 2. This construction is due to P. P.
Ewald.
10
 BRILLOUIN ZONES
Brillouin gave the statement of the diffraction condition that is most
widely used in solid state physics, which means in the description of
electron energy band theory and of the elementary excitations of other
kinds.
A Brillouin zone is defined as a Wigner-Seitz primitive cell in the
reciprocal lattice.
The Brillouin zone gives a vivid geometrical interpretation of the
diffraction condition 𝟐𝐤 ∙ 𝑮 = 𝐺 2 .
2
1 1
𝐤∙ 𝑮 = 𝐺 (26)
2 2
Take (23) divided by 4 at both sides
11
Plane 1 Plane 2
Figure 9a Reciprocal lattice points near the
point O at the origin of the reciprocal lattice.
The reciprocal lattice vector 𝑮𝐶 connects points
OC; and 𝑮𝐷 connects OD. Two planes 1 and 2
are drawn which are the perpendicular bisectors
of 𝑮𝐶 and 𝑮𝐷 , respectively. Any vector from the
origin to the plane 1, such as 𝐤1 , will satisfy the
1 1 2
diffraction condition 𝐤 𝟏 ∙ 𝑮 = 𝐺 .
2 𝑪 2 𝐶
Any vector from the origin to the plane 2, such
as 𝐤 2 , will satisfy the diffraction condition 𝐤 𝟐 ∙
1 1 2
𝑮 = 𝐺 .
2 𝑫 2 𝐷

12
 The set of planes that are the perpendicular bisectors of the reciprocal lattice vectors
is of general importance in the theory of wave propagation in crystals. A wave whose
wavevector drawn from the origin terminates on any of these planes will satisfy the
condition for diffraction.
These planes divide the Fourier space of the crystal into fragments, as shown in Fig.
9b for a square lattice. The central square is a primitive cell of the reciprocal lattice. It is a
Wigner-Seitz cell of the reciprocal lattice.
Figure 9b Square reciprocal lattice with
reciprocal lattice vectors shown as fine
black lines. The lines shown in white are
perpendicular bisectors of the reciprocal
lattice vectors. The central square is the
smallest volume about the origin which is
bounded entirely by white lines. The
square is the Wigner-Seitz primitive cell of
the reciprocal lattice. It is called the first
the first Brillouin zone Brillouin zone. 13
 The central cell in the reciprocal lattice is of special importance in the
theory of solids, and we call it the first Brillouin zone. The first Brillouin zone is
the smallest volume entirely enclosed by planes that are the perpendicular
bisectors of the reciprocal lattice vectors drawn from the origin.
The first Brillouin zone of an oblique lattice in two dimensions is
constructed in Fig. 10, and of a linear lattice in one dimension in Fig. 11. The
zone boundaries of the linear lattice are at k = ±𝜋/a, where a is the primitive axis
of the crystal lattice.
Historically, Brillouin zones are not part of the language of x-ray
diffraction analysis of crystal structures, but the zones are an essential part of the
analysis of the electronic energy-band structure of crystals.

14
 1st BZ & WS Primitive Cells
Figure 11
Wigner-Seitz The WS cell of
primitive cell in the BCC lattice
the reciprocal
lattice is a trunctuated
octohedron
1st BZ

The WS cell of
the FCC lattice is a
rhombic
dodecohedron
The reciprocal lattices (dots) and
corresponding first Brillouin zones
the first Brillouin zone
of (a) square lattice and
2-D oblique lattice (b) hexagonal lattice. 15
 1-D lattice

the first Brillouin zone

Figure 11 Crystal and reciprocal lattices in one dimension. The basis vector in the
reciprocal lattice is b, of length equal to 2𝜋Τ𝑎. The shortest reciprocal lattice vectors
from the origin are b and -b. The perpendicular bisectors of these vectors form the
boundaries of the first Brillouin zone. The boundaries are at k = ± 𝜋Τ𝑎 .
16
 Summaries of the Brillouin Zone, Wigner-Seitz Primitive Cell, &
Reciprocal Lattice
➢ Brillouin Zone (BZ) describes the area occupied in a reciprocal
space and it is defined as a Wigner-Seitz primitive cell in 2D or
3D.
➢ The first BZ is the smallest volume entirely enclosed by planes that
are the perpendicular bisectors of the reciprocal lattice vectors drawn
from the origin.
➢ The BZs are an essential part of the analysis of the electronic
energy-band structure of crystals.
➢ The BZ gives a geometrical interpretation of the diffraction
condition of a lattice.
17
 Reciprocal Lattices to Simple Cubic (SC)
The primitive translational vectors
Lattice constant, 𝑎
𝐚1 = 𝑎𝐱ො
z
𝐚2 = 𝑎𝐲ො
(27a)
𝑎 y 𝐚3 = 𝑎ො𝐳
x 𝑉 = 𝐚1 ∙ 𝐚2 × 𝐚3 = 𝑎3
The primitive translational vectors of the
reciprocal lattice
Lattice constant, 2𝜋Τ𝑎
𝐛1 = 2𝜋Τ𝑎 𝐱ො
kz
𝐛2 = 2𝜋Τ𝑎 𝐲ො (27b)
2𝜋Τ𝑎
ky
𝐛3 = 2𝜋Τ𝑎 𝐳ො
𝑎 kx
𝑉 = 𝐛1 ∙ 𝐛2 × 𝐛3 = 2𝜋Τ𝑎 3
18
 The boundaries of the first Brillouin zones are the planes normal to the six
reciprocal lattice vectors ±𝐛1 , ±𝐛2 , ±𝐛3 at their midpoints:
1 1 1
± 𝐛1 = ± 𝜋Τ𝑎 𝐱ො , ± 𝐛2 = ± 𝜋Τ𝑎 𝐲, ො ± 𝐛3 = ± 𝜋Τ𝑎 𝐳ො, (28)
2 2 2
The six planes bound a cube of edge and of volume this cube is the first Brillouin
zone of the sc crystal lattice.
Draw planes perpendicular to
Note that the arrangement of point In reciprocal space the lines connecting to the
is similar to a 2-D square lattice lattice points. The central
cube makes up the 1st BZ
𝐛3

2
𝐛2
a

𝐛1

19
 Reciprocal Lattices to Body Centered Cubic (BCC)
The primitive translational vectors
𝐚1 = 𝑎Τ2 −ො𝐱 + 𝐲ො + 𝐳ො
𝐚2 = 𝑎Τ2 𝐱ො − 𝐲ො + 𝐳ො (29)
𝐚3 = 𝑎Τ2 𝐱ො + 𝐲ො − 𝐳ො
𝑉 = 𝐚1 ∙ 𝐚2 × 𝐚3 = 𝑎Τ2 𝑎3 (30)

The primitive translational vectors of the reciprocal lat

𝐚2 × 𝐚3
𝐛1 = 2𝜋 = 2𝜋Τ𝑎 𝐲ො + 𝐳ො
𝐚1 ∙ 𝐚2 × 𝐚3
𝐛2 = 2𝜋Τ𝑎 𝐱ො + 𝐳ො (31)
𝐛3 = 2𝜋Τ𝑎 𝐱ො + 𝐲ො
Figure 12 Primitive basis vectors 𝑉 = 𝐛1 ∙ 𝐛2 × 𝐛3 = 2 2𝜋Τ𝑎 3
of the body-centered cubic lattice. 20
 The general reciprocal lattice vector is, for integral 𝑣1 , 𝑣2 , 𝑣3 ,
𝐆 = 𝑣1 𝐛1 + 𝑣2 𝐛2 + 𝑣3 𝐛3 (32)
The shortest 𝐆′ s are the following 12 vectors, where all choices of sign
are independent:
2𝜋Τ𝑎 ±𝐲ො ± 𝐳ො ; 2𝜋Τ𝑎 ±ො𝐱 ± 𝐳ො ; 2𝜋Τ𝑎 ±ො𝐱 ± 𝐲ො (33)
One primitive cell of the reciprocal lattice is the parallelepiped described
by the 𝐛1 , 𝐛2 , 𝐛3 defined by (31). The volume of this cell in reciprocal
space is 𝐛1 ∙ 𝐛2 × 𝐛3 = 2 2𝜋Τ𝑎 3 . The cell contains one reciprocal
lattice point, because each of the eight corner points is shared among
eight parallelepipeds. Each parallelepiped contains one-eighth of each of
eight corner points (Fig. 12).
21
 Another primitive cell is the central (Wigner-Seitz)
cell of the reciprocal lattice which is the first
Brillouin zone. Each such cell contains one lattice
point at the central point of the cell. This zone (for
the bcc lattice) is bounded by the planes normal to
the 12 vectors of Eq. (33) at their midpoints. The
zone is a regular 12-faced solid, a rhombic
dodecahedron, as shown in Fig. 13.

dodecahedron
Figure 13 First Brillouin zone of the
body-centered cubic lattice. The figure is a
regular rhombic dodecahedron.
22
 Reciprocal Lattices to Face Centered Cubic (FCC)
The primitive translational vectors
𝐚1 = 𝑎Τ2 𝐲ො + 𝐳ො
𝐚2 = 𝑎Τ2 𝐱ො + 𝐳ො (34)
𝐚3 = 𝑎Τ2 𝐱ො + 𝐲ො
𝑉 = 𝐚1 ∙ 𝐚2 × 𝐚3 = 𝑎Τ4 𝑎3 (35)

The primitive translational vectors of

the reciprocal lattice
𝐛1 = 2𝜋Τ𝑎 −ො𝐱 + 𝐲ො + 𝐳ො
𝐛2 = 2𝜋Τ𝑎 𝐱ො − 𝐲ො + 𝐳ො (36)
𝐛3 = 2𝜋Τ𝑎 𝐱ො + 𝐲ො − 𝐳ො
Figure 14 Primitive basis vectors of the 3
face-centered cubic lattice. 𝑉 = 𝐛1 ∙ 𝐛 2 × 𝐛3 = 4 2𝜋 Τ𝑎
23
These are primitive translation vectors of a bcc lattice, so that the bcc
lattice is reciprocal to the fcc lattice.
The shortest G’s are the eight vectors:
2𝜋Τ𝑎 ±ො𝐱 ± 𝐲ො ± 𝐳ො (37)
The boundaries of the central cell in the reciprocal lattice are determined
for the most part by the eight planes normal to these vectors at their
midpoints. But the corners of the octahedron thus formed are cut by the
planes that are the perpendicular bisectors of six other reciprocal lattice
vectors:
2𝜋Τ𝑎 ±2ො𝐱 ; 2𝜋Τ𝑎 ±2𝐲ො ; 2𝜋Τ𝑎 ±𝟐ො𝒛 (38)
Note that 2𝜋Τ𝑎 ±2ො𝐱 is a reciprocal lattice vector because it is equal
to 𝐛𝟐 + 𝐛3 .
24
 The first Brillouin zone is the
smallest bounded volume about
the origin, the truncated
octahedron shown in Fig. 15. The
six planes bound a cube of edge
4𝜋Τ𝑎 and (before truncation) of
volume 4 2𝜋Τ𝑎 3 .

Figure 15 Brillouin zones of the face-centered cubic

octahedron lattice. The cells are in reciprocal space, and the
reciprocal lattice is body-centered.
25
BCC Primitive Lattice Reciprocal Lattice The first Brillouin zones

4
a a
FCC

4
a 4 a
a

26
The first Brillouin zones of BCC and FCC

BCC FCC 27
 Critical Points of Several Crystal Structures
Symbol Description
Γ Center of the Brillouin zone
Simple cube
M Center of an edge
R Corner point
X Center of a face
Face-centered cubic
Middle of an edge joining two
K
hexagonal faces
L Center of a hexagonal face
Middle of an edge joining a
U
hexagonal and a square face
W Corner point
X Center of a square face
Body-centered cubic
H Corner point joining four edges
N Center of a face
P Corner point joining three edges
Hexagonal
A Center of a hexagonal face
H Corner point
Middle of an edge joining two
K
rectangular faces
Middle of an edge joining a
L
hexagonal and a rectangular face
28
M Center of a rectangular face
Figure 10. (a–c) are the
schematics of the SC, BCC,
FCC lattices and the
corresponding primitive cells.
(d–f) Show the design domains
that are actually used in the
sensitivity analyses. (g–i) are
the first Brillouin zones of the
three cubic lattices. The red
regions inside the Brillouin
zones are the IBZs.

29
Summaries of Primitive and Reciprocal Lattices
Primitive vectors Reciprocal vectors

Cube Cube
Vectors Volume Vectors Volume
edge edge
2𝜋
𝑏1 = 𝑥
𝑎1 = 𝑎𝑥 𝑎
Simple 2𝜋
𝑎2 = 𝑎𝑦 𝑎 𝑎3 𝑏2 =
𝑎
𝑦 2𝜋Τ𝑎 2𝜋Τ𝑎 3
Cubic 𝑎3 = 𝑎𝑧
2𝜋
𝑏3 = 𝑧
𝑎
𝑎 2𝜋
𝑎1 = 𝑥+𝑦−𝑧 𝑏1 = 𝑦+𝑧
Body 2 𝑎
𝑎 𝑎 1 3 2𝜋 3
Centered 𝑎2 =
2
−𝑥 + 𝑦 + 𝑧 𝑎 𝑏2 = 𝑥+𝑧 4𝜋Τ𝑎 2 2𝜋Τ𝑎
2 𝑎
Cubic 𝑎 2𝜋
𝑎3 = 𝑥−𝑦+𝑧 𝑏3 = 𝑥+𝑦
2 𝑎
𝑎 2𝜋
𝑎1 = 𝑦+𝑧 𝑏1 = −𝑥 + 𝑦 + 𝑧
Face 2 𝑎
𝑎 𝑎 1 3 2𝜋 3
Centered 𝑎2 = 𝑥 + 𝑧
2 𝑎 𝑏2 = 𝑥−𝑦+𝑧 4𝜋Τ𝑎 4 2𝜋Τ𝑎
4 𝑎
Cubic 𝑎 2𝜋
𝑎3 = 𝑥+𝑦 𝑏3 = 𝑥+𝑦−𝑧
2 𝑎
30
 FOURIER ANALYSIS OF THE BASIS
When the diffraction condition ∆𝐤 = 𝐆 is satisfied, the scattering
amplitude for a crystal of 𝑁 cells:

𝐹 = න 𝑑𝑉 𝑛 𝐫 exp −𝑖∆𝐤 ∙ 𝐫 = න 𝑑𝑉 𝑛 𝐫 exp −𝑖𝐆 ∙ 𝐫 = 𝑁𝑆𝐺

𝑐𝑒𝑙𝑙
The quantity 𝑆𝐺 is called the structure factor and is defined as an integral
over a single cell, with 𝐫 = 0 at one corner.
If 𝐫𝑗 is the vector to the center of atom 𝑗, then the function 𝑛𝑗 𝐫 − 𝐫𝑗
defines the contribution of that atom to the electron concentration
at 𝐫.

31
The total electron concentration at 𝐫 due to all atoms in the single cell is the
sum
𝑠

𝑛 𝐫 = ෍ 𝑛𝑗 𝐫 − 𝐫𝑗
𝑗−1
over the 𝑠 atoms of the basis.
The structure factor defined by (39) may now be written as integrals
over the s atoms of a cell:

𝑆𝐺 = ෍ න 𝑑𝑉 𝑛𝑗 𝐫 − 𝐫𝑗 exp −𝑖𝐆 ∙ 𝐫
𝑗

= ෍ exp −𝑖𝐆 ∙ 𝐫𝑗 න 𝑑𝑉 𝑛𝑗 𝝆 exp −𝑖𝐆 ∙ 𝝆

𝑗
where 𝝆𝐫 − 𝐫𝑗 32
We now define the atomic form factor:

𝑓𝑗 = න 𝑑𝑉 𝑛𝑗 𝝆 exp −𝑖𝐆 ∙ 𝝆

integrated over all space. If 𝑛𝑗 𝝆 is an atomic property, 𝑓𝑗 is an atomic

property.
We combine (41)and (42) to obtain the structure factor of the basis in
the form:

𝑆𝐺 = ෍ 𝑓𝑗 exp −𝑖𝐆 ∙ 𝐫𝑗
𝑗
The usual form of this result follows on writing for atom j:
𝐫𝑗 = 𝑥𝑗 𝐚1 + 𝑦𝑗 𝒂2 + 𝑧𝑗 𝒂3
as in (1.2).
33
Then, for the reflection labelled by 𝜐1 , 𝜐2 , 𝜐3 , we have
𝐆 ∙ 𝐫𝑗 = 𝜐1 𝐛1 + 𝜐2 𝐛2 + 𝜐3 𝐛3 ∙ 𝑥𝑗 𝐚1 + 𝑦𝑗 𝒂2 + 𝑧𝑗 𝒂3
= 2𝜋 𝜐1 𝑥𝑗 + 𝜐2 𝑦𝑗 + 𝜐3 𝑧𝑗
so that (43) becomes

𝑆𝐺 𝜐1 𝜐2 𝜐3 = ෍ 𝑓𝑗 exp −𝑖2𝜋 𝜐1 𝑥𝑗 + 𝜐2 𝑦𝑗 + 𝜐3 𝑧𝑗
𝑗

The structure factor 𝑆 need not be real because the scattered intensity will
involve 𝑆 ∗ 𝑆, where 𝑆 ∗ is the complex conjugate of 𝑆 so that 𝑆 ∗ 𝑆 is real.

34
 At a zero of 𝑆𝐺 the scattered intensity will be zero, even though 𝐆
is a perfectly good reciprocal lattice vector. What happens if we choose
the cell in another way, as a conventional cell instead of a primitive cell,
for example? The basis is changed, but in such a way that the physical
scattering is unchanged. Thus for two choices, 1 and 2, it is not hard to
satisfy yourself from (39) that
𝑁1 𝑐𝑒𝑙𝑙 × 𝑆1 𝑏𝑎𝑠𝑖𝑠 = 𝑁2 𝑐𝑒𝑙𝑙 × 𝑆2 𝑏𝑎𝑠𝑖𝑠

35
 Structure Factor of the bcc Lattice
The bcc basis referred to the cubic cell has identical atoms at
1
𝑥1 = 𝑦1 = 𝑧1 = 0 and at 𝑥2 = 𝑦2 = 𝑧2 = . Thus (46) becomes
2

𝑆𝐺 𝜐1 𝜐2 𝜐3 = 𝑓 1 + exp −𝑖𝜋 𝜐1 + 𝜐2 + 𝜐3
where 𝑓 is the form factor of an atom. The value of 𝑆 is zero
whenever the exponential has the value −1, which is whenever
the argument is −𝑖𝜋 × (odd integer). Thus
𝑆=0 when 𝜐1 + 𝜐2 + 𝜐3 = odd integer ;
𝑆 = 2𝑓 when 𝜐1 + 𝜐2 + 𝜐3 = even integer ; Sodium Crystal Structure
Metallic sodium has a bcc structure. The diffraction pattern does
not contain lines such as (100), (300), (111), or (221), but lines
such as (200), (110), and (222) will be present; here the indices
𝜐1 𝜐2 𝜐3 are referred to a cubic cell.
36
37
 Structure Factor of the fcc Lattice
The basis of the fcc referred to the cubic cell has identical atoms
11 1 1 11
at 000; 0 ; 0 ; 0. Thus (46) becomes
22 2 2 22
𝑆𝐺 𝜐1 𝜐2 𝜐3
= 𝑓ሼ1 + exp −𝑖𝜋 𝜐2 + 𝜐3 + exp −𝑖𝜋 𝜐1 + 𝜐3
+ exp −𝑖𝜋 𝜐1 + 𝜐2 ሽ
✓ If all indices are even integers, 𝑆 = 4𝑓; similarly if all indices
are odd integers.
✓ But if only one of the integers is even, two of the exponents will
be odd multiples of −𝑖𝜋 and 𝑆 will vanish.
Potassium Chloride
✓ If only one of the integers is odd, the same argument applies Crystal Structure
and 𝑆 will also vanish.
✓ Thus in the fcc lattice no reflections can occur for which the
indices are partly even and partly odd. 38
39
 Atomic Form Factor
𝑆𝐆 𝜐1 𝜐2 𝜐3 = ෍ 𝑓𝑗 exp −𝑖2𝜋 𝜐1 𝑥𝑗 + 𝜐2 𝑦𝑗 + 𝜐3 𝑧𝑗
𝑗

❑ There occurs the quantity 𝑓𝑗 , which is a measure of the scattering

power of the 𝑗th atom in the unit cell.
❑ The value of 𝑓 involves the number and distribution of atomic
electrons, and the wavelength and angle of scattering of the radiation.
❑ We now give a classical calculation of the scattering factor. The
scattered radiation from a single atom takes account of interference
effects within the atom.

𝑓𝑗 = න 𝑑𝑉 𝑛𝑗 𝐫 exp −𝑖𝐆 ∙ 𝐫
40
❑ If the electron distribution is spherically symmetric about the origin,

𝑓𝑗 ≡ 2𝜋 න 𝑑𝑟 𝑟 2 𝑑 cos 𝛼 𝑛𝑗 𝑟 exp −𝑖𝐺𝑟 cos 𝛼

𝑒 𝑖𝐺𝑟 − 𝑒 −𝑖𝐺𝑟
= 2𝜋 න 𝑑𝑟 𝑟 2 𝑛𝑗 𝑟 ∙
𝑖𝐺𝑟

after integration over 𝑑 cos 𝛼 between 1 and 1,

sin 𝐺𝑟
𝑓𝑗 = 4𝜋 න 𝑑𝑟 𝑛𝑗 𝑟 𝑟2 =
𝐺𝑟

If the same total electron density were concentrated at 𝑟 = 0, only

𝐺𝑟 = 0 would contribute to the integrand.
41
In this limit sin 𝐺𝑟Τ𝐺𝑟, and

𝑓𝑗 = 4𝜋 න 𝑑𝑟 𝑛𝑗 𝑟 𝑟 2 = 𝑍

the number of atomic electrons. Therefore f is the ratio of the radiation amplitude
scattered by the actual electron distribution in an atom to that scattered by one
electron localized at a point. In the forward direction 𝐺 = 0, and 𝑓 reduces again to
the value 𝑍.

The overall electron distribution in a solid as seen in x-ray diffraction is

fairly close to that of the appropriate free atoms.

42
Remark:
This statement does not mean that the outermost or valence electrons are
not redistributed somewhat in forming the solid; it means only that the x-
ray reflection intensities are represented well by the free atom values of the
form factors and are not very sensitive to small redistributions of the
electrons.

43
 Try out……

1. Structure factor of diamond. The crystal structure of diamond is

described in Chapter 1. The basis consists of eight atoms if the cell
is taken as the conventional cube. (a) Find the structure factor 𝑆 of
this basis. (b) Find the zeros of 𝑆 and show that the allowed
reflections of the diamond structure satisfy 𝜐1 + 𝜐2 + 𝜐3 = 4𝑛,
where all indices are even and 𝑛 is any integer, or else all indices are
odd (Fig. 18). (Notice that ℎ, 𝑘, 𝑙 may be written for 𝜐1 , 𝜐2 , 𝜐3 and
this is often done.)

44
45
Summary for cubic and hexagonal lattices

46
Crystal structure of for the most
common metallic elements

47