1

Structure Factors

H. Garmestani
Ref: Elements of X-ray Diffraction, Third Edition , by B.D. Cullity and S.R. Stock
Chapter 4: 4-4 to 4-6

Outline:
Structure Factor
Atomic Scattering Factor
The Fourier Transform (Compression
extension property)
Atomic scattering factors for electrons
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X-ray Spectroscopy

• Bragg’s Law:
– To determine d-spacing: apply an x-ray of known
wavelength and measuring q. Method called
STRUCTURE ANALYSIS
– A crystal of known
d-spacing can be used to
measure q, and thus
the wavelength.
X-ray Spectroscopy
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XRD Graph

• Recall an X-ray Diffraction gives a graph

like this:

Different Peaks have different

Intensities
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Intro ( ) ∫
f ( a) K =
atom
( a)
ρatom ( )
x e− iK ⋅x d 3 x

• The amplitude of scattering providing us with the observed

intensity, is a function of S. The amplitude is then the
Fourier Transform of the scattering density.
N1 −1 N 2 −1 N 3 −1
iK .rj
F crystal (K ) = [∑ f j (K )e ][ ∑ eiK .n1a ∑ e iK .n2 b
∑ e iK .n3 c
]
rj n1 = 0 n2 = 0 n3 = 0
StructureFactor LatticeSum
where,

Rn = n1a1 + n2 a2 + n3a3
or, Where, f is the atomic form factor

#   & N1 −1  2
N −1 N 3 −1
F Crystal (Q) = % ∫ ρ(ro )eiQ.ro dVro ( ∑ eiQ.n1a1 ∑ eiQ.n2 a2 ∑ eiQ.n3 a3
%$Vro (' n1 = 0 n2 = 0 n3 = 0
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Intensity of XRD Peaks

• Also recall that the Intensity of peaks depends

on many factors:

1 + cos ( 2q )
2
2
I= F p 2 A(q )e -2 M

sin (q ) cos(q )
Where F is the structure factor

It is dependent on the crystal lattice and the chosen

plane
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d-spacing and Multiplicity, p

Crystal Planes

Four Planes
111 8 of (111) for a
100 6 total of 8

110 12
311 24
222 8
400 6
331 24
6
420 24
 d-spacing and Multiplicity, p 7

https://www.doitpoms.ac.uk/tlplib/miller_indices/lattice.php

Crystal Planes

p six planes of {100}

111 8
100 6
110 12
311 24
222 8 12 planes of {110}
400 6
331 24
7
420 24
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Allowed and forbidden Reflections

• In some cases (BCC, FCC,…) some planes

of lattice points may give rise to destructive
interference, reducing the Intensity of
diffracted X-rays
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Structure Factor

N
Fhkl = ∑ f n e 2 πi(hun +kv n +lw n )

1
• Fhkl is the Structure Factor
• fn is the atomic factor

Note that :
*the structure factor is only defined for specific miller indices (hkl).
*The absolute Value of |F| gives the amplitude of the resultant wave in
terms of the amplitude of the wave scattered by a single electron
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Structure Factor

N
Fhkl = ∑ fn e
2 π i( h un + kv n +lwn )

• The absolute Value of |F| gives the amplitude of

the resultant wave in terms of the amplitude of the
wave scattered by a single electron
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Complex Numbers
i = -1
i1 = i i 2 = -1 i 3 = -i i4 = 1

-7 = i 7
-160 = 4i 10
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Complex Variables i = -1

We here go through the complex algebra briefly.

A complex number z = (x,y) = x + iy, Where.

x: the real part, labeled by Re(z);

y: the imaginary part, labeled by Im(z)

Three frequently used representations:

(1) Cartesian representation: x+iy

(2) polar representation, we may write z = r × e iq

z=r(cosqi sinqor

r – the modulus or magnitude of z

q- the argument or phase of z
12
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Complex Fourier Series

• Remember that each wave can be represented as a sinusoidal wave of

the form:

E3

• Where no=wo/2p Then,

E1

E2
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Complex Fourier Series

• The complex form is obtained by substituting the

exponential equivalent of the sin and cosine terms

• or,

• Note that,
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Complex Fourier Series

• Same can be represented by the use of complex numbers, where the

amplitude and the phase can be given by A and f:

• Then,
A
f
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Example-Structure Factor (Cullity)

Cubic Structure

• Let’s consider a simple case of a cubic unit cell containing

8 atoms in the 8 corners but only one atom at the origin as
the basis, or 000
• This means u1=u2=u3=0 and its structure factor is then
N
Fhkl = ∑ fn e
2 π i( h un + kv n +lwn ) 2πi (0 )
= fe =f
1

• Then |F| is independent of hkl and is the same for all

reflections,
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Example-Structure Factor (Cullity)

Base Centered cell

• It has two atoms of the same kind per unit cell located at
000 and 1/2 1/2 0.

N
Fhkl = ∑ fn e
2 π i( h un + kv n +lwn )
=
1
2 π i( 0 ) 2 π i( h/ 2 +k /2 )
= fe + fe
πi( h+ k )
= f (1+ e )
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Example-Structure Factor (Cullity)

Base Centered cell
• Since h+k is always integer, the expression for F is always
real
• This is true from Euler’s Equation:
e ni = cos(n ) + i sin(n )
Thus for Base-Centered Cell:
epi ( h + k ) = cos(p ( h + k ) ) + i sin(p ( h + k ) )
If h+k is odd:
cos(p ( h + k )) = -1
If h+k is even:
cos(p ( h + k )) = 1

= (- 1) = (- 1)
pi ( h + k ) ( h+k ) n
THUS: e
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Example-Structure Factor (Cullity)

Base Centered cell

• If h+k are both odd or even, then F=2f and F2=4f2

• If h+k are mixed, F=0 and F2=0.
• In any of these cases the value of l index has no effect on
the structure factor
• Example:
– 111, 112, 113, and 021, 022, 023 have the same reflection
– 011, 012, 013 and 101, 102, 103 have zero reflections
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Example-Structure Factor (Cullity)

Body Centered cell(BCC)

• Two atoms of the same kind at 000, and 1/2 1/2 1/2
N
Fhkl = ∑ fn e 2πi h un + kv n +lwn =
( )

1
πi( h+ k +l )
= f (1+ e )

• If h+k+l=even, F=2f and F2=4f2

• If h+k+l=odd F=0 and F2=0.
• Note: base centered cubic produces
• a 001 reflection but BCC will not
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Example-Structure Factor (Cullity)

Face Centered cell(FCC)

• Contains four atoms of the same kind, located at 000, 1/2

1/2 0, 1/2 0 1/2, and 0 1/2 1/2
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Example-Structure Factor (Cullity)

Face Centered Cell (FCC)
r1 = 0
• 000, 1/2 1/2 0, 1/2 0 1/2, and 0 1/2 1/2 1
r2 = (a1 + a2 )
2
N 1
Fhkl = ∑ fn e 2 π i(hun +kvn +lwn )
=
r3 = (a2 + a3 )
2
1
1 r4 = (a1 + a3 )
2
2 π i(0) 2 π i(h/2+k/2) 2 π i(h/2+l/2) 2 π i(k/2+l/2)
= fe + fe + fe + fe
π i(h+k ) π i(h+l ) π i(k+l )
= f (1 + e +e +e )
• If all are unmixed (odd and odd, even and even), then each
term has a value of 1: F=4f,
• If all are mixed (odd and even), then each term has a value
of -1 or +1 depending on the mixture: F=0 for 012,
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Example-Structure Factor (Cullity)

Face Centered Cell (FCC)
r1 = 0
• 000, 1/2 1/2 0, 1/2 0 1/2, and 0 1/2 1/2, or, 1
r2 = (a1 + a2 )
2
1
r3 = (a2 + a3 )
N 2
Fhkl = ∑ f n e 2 πi(hun +kv n +lw n )
= 1
r4 = (a1 + a3 )
2
1
2 πi(0) 2 πi(h / 2+k / 2) 2 πi(h / 2+l / 2) 2 πi(k / 2+l / 2)
= fe + fe + fe + fe
πi(h +k ) πi(h +l ) πi(k +l )
= f (1+ e +e +e )
•If all are unmixed (odd and odd, even and even), then each term has a value of 1: F=4f,
If all are mixed (odd and even), then each term has a value of -1 or +1 depending on the mixture:
•012, F=0 for
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Example-Structure Factor (Cullity)

Face Centered Cell (FCC)
π i(h+k ) π i(h+l ) π i(k+l )
Fhkl = f (1 + e +e +e )
• If all are unmixed (odd and odd, even and even), then each
term has a value of 1: F=4f,
• If all are mixed (odd and even), then each term has a value
of -1 or +1 depending on the mixture: F=0 for 012,
epi ( h + k ) = (- 1) = (- 1)
( h+k ) n
• Remember:
• {111}, {200}, {113}, {220} gives 4f
• {100}, {110}, {012} gives zero
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Structure Factor
• Structure Factor is independent of the size and shape of the
unit cell.
• Any body centered cell will have missing reflections for
those planes which have (h+k+l) equal to an odd number,
whether the cell is cubic, tetragonal or orthorhombic

Bravais Lattice Reflections Possibly present Reflections necessarily

absent
Simple all none
Base centered h and k unmixed h and k mixed
Body centered (h+k+l) even (h+k+l) odd
Face Centered h, k, and l unmixed h, k, and l mixed
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HMW#6, Problem#2
• A certain tetragonal crystal has four atoms of the same
kind per unit cell, located at 0 1/2 1/4, 1/2 0 1/4, 1/2 0
3/4, 0 1/2 3/4, (Do not change axes),
a) Derive simplified expressions for F2
b) What are the values of F2 for the 100, 002, 111, and 011 reflections.

N 4
Fhkl = ∑ fn e2 π i(hun + kvn +lwn ) = ∑ fn e2 π i(hun + kvn +lwn ) =
1 1

= fe2 π i(k /2 +l / 4 ) + fe2 π i(h /2 +l / 4 ) + fe2 π i(h /2 + 3l / 4 ) + fe2 π i(k /2 + 3l /2)

= f (eπ i(k +l /2) + eπ i(h +l /2) + eπ i(h + 3l /2) + eπ i(k + 3l /2) )
= feπ i(l /2) (eπ ik + eπ ih + eπ i(h +l ) + eπ i(k +l ) )
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• And,…

N
Fhkl = ∑ fn e2 π i(hun + kvn +lwn ) =
1

= feπ i(l /2) (eπ ik + eπ ih + eπ i(h +l ) + eπ i(k +l ) )

= feπ i(l /2) ⎡⎣ eπ ik (1 + eπ il ) + eπ ih (1 + eπ il ) ⎤⎦
= feπ i(l /2) (1 + eπ il )(eπ ik + eπ ih )
•If l is an odd number the first (..) becomes zero.
•In h and k are mixed (even and odd or odd and even), the second term
also becomes zero.
•I think you can get the picture for the rest…
•Next is to get F2,
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Example-Structure Factor for NaCl

• Lattices interpenetrating (Na on FCC

lattice,Cl on FCC lattice)
11 1 1 11
– Na at 000
22
0 0
2 2
0
22
1 11 1 1 1
– Cl at 2 22
0 0
2
00
2 2
00
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Example-Structure Factor for NaCl

• Total Structure factor FTotal = FN a + FCl

F = f N a[1+ exp(2πi (h / 2 + k / 2)) + exp2πi(k / 2 + l / 2 ) + exp 2πi (h / 2 + l / 2)]

+ fCl[exp( 2πi( h / 2 + k / 2 + l / 2)) + exp (2πi (l / 2 )) + exp(2πi( k / 2 )) + exp( 2πi( h / 2))

Or,

F = f N a[1+ exp(πi (h + k )) + exp πi( k + l ) + exp πi( h + l )]

+ fCl[exp(πi(h + k + l )) + exp(πi (l )) + exp(πi( k )) + exp(πi(h))
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Example-Structure Factor for NaCl

• Factoring out the translation vector

F = f N a[1+ exp(πi (h + k )) + exp πi( k + l ) + exp πi( h + l )]
+ fCl exp(πi(h + k + l))[1+ exp(πi (−h − k )) + exp(πi( −h − l )) + exp (πi( −k − l ))
Since the complex exponents simplify to a single cosine function,

eπi(-h-k)=eπi(h+k)
F = [1 + exp (πi( h + k )) + exp πi(k + l ) + exp πi(h + l )]
x[ f N a + fCl .exp(πi (h + k + l ))]
This means that F can be calculated as a combination of two
factors=
translation components x basis component
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Example-Structure Factor for NaCl

[
F = 1+e πi ( h+ k )
+e π i ( k + l)
+e πi( h+ l)
].[ f Na + fCl .e πi( h+ k + l)
]
• For mixed indices, F=0 and F2=0
• For unmixed indices F=4[fNa+fClepi(h+k+l)]
– If h+k+l=even F=4[fNa+fCl], F2=4[fNa+fCl]2,
– If h+k+l=odd F=4[fNa-fCl], F2=4[fNa-fCl]2,

• Note: Four atoms per unit cell, but the lattice is

still FCC-->increase in intensity
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Structure Factor
(General Procedure -Cullity)

• 1- Write down the atom positions as:

– Basis+Translation
– For NaCl: 4Na at 000+face-centering translations
– 4Cl at 1/2 1/2 1/2 +face-centering
translation
• 2- Write down the equations for F as a product of
two factors
(common translation components)(basis atoms)
For NaCl:
F=4[fNa+fClepi(h+k+l)] unmixed indices
F=0[fNa+fClepi(h+k+l)] mixed indices
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Atomic Scattering Factors

• Also known as the atomic form factor which

defines the main difference among x-ray, neutron,
and electron diffraction
– X-rays are scattered by electric field interactions with
the electrons
– Electrons are scattered by the variations in electric
potential within the specimen
– Neutrons are scattered by short range nuclear forces
and by magnetic dipole interaction with unpaired
electrons
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Resources of Added figures

• Dr. Y. Li, “Introduction to X-ray Diffraction,” Materials

Research Laboratory, University of California, Santa
Barbara, [Online Document] 2008 Apr 18, [cited 2007],
Available HTTP:
http://www.mrl.ucsb.edu/mrl/centralfacilities/xray/xray-
basics/index.html