1

Determination of Crystal Structure

H. Garmestani
Ref:Element of X-ray Diffraction,
Third Edition by Cullity&Stock
ch#4-13, 10
Outline:
Diffraction pattern
Intensity of Diffraction pattern
Indexing
Crystal Structure Determination (Ch#10)
…
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Diffraction Pattern

In general the structure determines the diffraction

pattern. Given a structure, the diffraction pattern can
be calculated! The question is whether the structure
can be determined from the diffraction pattern

Crystal Structure Diffraction Pattern

Unit Cell Line Positions

Atom Position Line intensities

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Intensity of Diffraction Peaks

• Hull/Debye-Scherrer Camera:
" 1 + cos2 2θ %
2 −2 M
I = F p$ 2 ' A(θ ) e
# sin θ cosθ &
• Diffractomer:
" 1 + cos2 2θ % −2M
2
I = F p$ 2 'e
# sin θ cosθ &
I=relative integrated intensity
F=Structure factor
p=multiplicity factor
q=Bragg angle
( )= Lorentz-polarization factor
A(q)= absorption factor
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Randomly Oriented Powder

• Two factors can make the above equations
invalid
– Preferred Orientation
– Extinction: The decrease in integrated intensity
as the crystals become larger in size (more
perfect). The structure is assumed to consist of
small mosaic blocks (of the order of 10-4cm to
10-5cm in thickness)
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Example
• (4-13 in Cullity) use the Hall/Debye-Scherrer
pattern of copper
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Copper -Cubic Structure

• Copper is cubic and for a cubic crystal, values of sin2q can
be calculated from 2
λ
sin θ = 2 ( h2 + k 2 + l 2 )
2

4a
• Remember that
l=1.542A and
a=3.615A (lattice parameter of copper)

• Then λ2
2 = 0.0455
4a
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Structure Factor for Cu

• Copper is FCC structure and contains four atoms of
the same kind located 1 1 1 1 11
000, 0, 0 ,0
2 2 2 2 22
• The calculation of the structure factor shows that
reflections can only occur for unmixed
combinations of h, k and l (all odd or all even):
(111), (200), (220), and is equal to

F = 4 f for unmixed indices

2 2
or F = 16 f
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Bragg angle Calculation for Cu

• Let’s go through the calculation of the very first
reflection, that of 111. The rest will follow the
same procedure!
• Bragg angle can be calculated from Bragg’s law
for each of the reflections
sin θ = 0.0455(h + k + l )
2 2 2 2

• This means that Sin2q=0.1365 for the 111

reflection
• Sinq=0.369 and then q is calculated to be 21.7
degrees
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Bragg angle Calculation for Cu

Line hkl h2+k2+l2 Sin2q Sinq q

1 111 3 0.1365 0.369 21.7
2 200 4 0.182 0.427 25.3
3 220 8 0.364 0.603 37.1
4 311 11 0.500 0.707 45.0
5 222 12 0.546 0.739 47.6
6 400 16 0.728 0.853 58.5
7 331 19 0.865 0.930 68.4
8 420 20 0-.910 0.954 72.6
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Lorentz Polarization Factor

• Include the polarization effect
1+ cos2 2θ
Lorentz− polarization Factor =
4sin2 θ cosθ

• The general effect is to

decrease the intensity of
reflections at intermediate
angles compared to those in
forward and backward
directions
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Intensity Calculation for Cu

• The Intensity calculation requires the knowledge of a few
parameters dependent on the structure as shown in
2" 1 + cos2 2θ % −2M
I = F p$ 2 'e
# sin θ cosθ &
• F2=16f 2Cu can be calculated from Appendix 10 in Cullity
which requires the calculation of sinq/l=0.24A-1. fCu=22.1
for Copper and F2=7810
• Multiplicity factor can be found in Appendix 11. For
111=>8
• Lorentz-Polarization factor can be calculated directly from
the equation or appendix 12. For 111(q=21.7) it
corresponds to 12.03
• Combining all in above equation, we get 7.52x105
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Intensity Calculation for Cu

• Summarizing
Line q Sinq/l(A-1) fCu F2 p " 1 + cos2 2θ %
$ 2 ' Intensity
# sin θ cosθ &

1 21.7 0.24 22.1 7810 8 12.03 7.52x103

2 25.3 0.27 20.9 6880 6 8.50 3.56
3 37.1 0.39 16.8 4520 12 3.70 2.01
4 45.0 0.46 14.8 3500 24 2.83 2.38
5 47.6 0.48 14.2 3230 8 2.74 0.71
6 58.5 0.55 12.5 2500 6 3.18 0.48
7 68.4 0.60 11.5 2120 24 4.81 2.45
8 72.6 0.62 11.1 1970 24 6.15 2.91
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Structure of ZnS
• Structure of ZnS is FCC, a=5.41A
• First determine the structure factor:
– ZnS has 4 Zn and 4 S atoms in the unit cell
1 11
Zn: + face − centering translations
4 44
S: 000 + face − centering translations
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Structure Factor for ZnS

• Now F is calculated as

[
F = 4 fS + fZne
(πi / 2 )( h +k + l)
]
• F2 is calculated by multiplying to the complex conjugate
2 ! 2 2 x $
F = 16 # f S + f Zn + 2 fZn fZn cos (h + k + l )&
" 2 %
• Special cases:

F = 16[ f + f ]
2 2 2
S Zn when ( h + k + l )is odd
F = 16[ fS − f Zn]
2 2
when (h + k + l ) is an odd multiple of 2
2
F = 16[ fS + fZn ] 2 when (h + k + l ) is aneven multiple of 2
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Intensity and Bragg angle
calculation for ZnS
λ2 2
• The Bragg angle is calculated from , where
sin θ = 2 ( h + k 2 + l 2 )
2

l=1.542A and a=5.41A, then

4a
which means
sin θ = 0.0203(h 2 + k 2 + l 2 )
2

q=14.3 for 111 reflection.

• Calculating Sin q / l =0.16, fS and fZn can be read from
Appendix 10 for both S and Zn.
• Structure factor is calculated as shown before
• Multiplicity factor,p, is read from Appendix 11.
• The Lorentz-Polarization factor is read from Appendix 12.
• The intensity can now be calculated from:

2" 1 + cos2 2θ % −2M

I = F p$ 2 'e
# sin θ cosθ &
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Reciprocal Space and Diffracted

• Bring the desired portions of the reciprocal space

into contact with the Ewald space
• Each hkl reflection has an intensity proportional to
the structure factor squared F2hkl.
• Consider the reciprocal Lattice for NaCl
– There are three values of structure factor is possible
F2 = 0 h, k, l mixed
2
16( f N a + fCl ) h, k, l unmixed,(h + k + l)is even
2
16( f N a − fCl ) h, k, l unmixed,(h + k + l)is odd
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Sampling of Reciprocal Space for
NaCl
§ Consider the 110
reciprocal lattice b1-b2 h, k, l mixed
plane Unmixed h+k+l even
§ The 110 reciprocal Unmixed h+k+l odd
lattice plane of
NaCl contains hkl
of all three types,
and these are
indicated in the
figure.

b1
000 001 002 003 004
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Crystal Structure Determination

• Three steps:
1) Shape and size of the Unit cell are deduced from the
angular positions of the diffraction lines
a) An assumption is made as to the 7 crystal systems
b) “INDEXING: Miller indices are assigned to each reflection.
2) The Number of atoms/unit cell are deduced from the
shape and size of the unit cell.
a) Chemical composition
b) Measured intensity
3) Position of the atoms are deduced from the relative
intensities of the diffraction lines.
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Preliminary Treatment of Data

• Record the diffraction pattern over a wide range of
2q.
• After the pattern is obtained the values of sin2q is
calculated for each diffracted line
• The structure determination is to account for all the
diffraction lines (both in position and the intensity)
• Two sources of error:
1) Wavelengths other than the principal component
2) Diffraction by substances other than the unknown
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Radiation other than Ka

• In general a filtered radiation is used and Ka is the
principal component.
• The chief offender is Kb radiation which results in the
same d-spacing and from the Bragg’s law
$ λ2Kα ' 2 2
& λ2 ) sin θ β = sin θα
% Kβ (
• where λ 2Kα / λ 2Kβ = 1.2
and Kb radiation line always occurs at a
smaller angle with a smaller intensity. Multiplying the
corresponding sin2q by 1.2 will give a value equal to sin2q
for Ka.
• Other sources of error may involve L Characteristics lines
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Systematic error in sin2q

• Small but can be removed by examining a

specimen of known d-spacing mixed with the
unknown.
• The difference between the observed and
calculated can result in a correction curve of the
kind as shown in the figure

Figure 10.1 from C&S

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Indexing Patterns of Cubic Crystals

• Using the d-spacing for a cubic crystal in the equation

for the Bragg’s law: 2
sin θ
=
2 2
sin θ
=
λ
(h + k + l ) s 4a
2 2 2 2

• Since s is an integral and λ2 / 4a2 is a constant for any

one pattern, indexing requires finding a set of integers
s which will yield a constant quotient when divided
one by one into the observed sin2q values
• Remember that certain integers like 7, 15, 23, 28, 31
are impossible because they cannot form h 2 + k 2 + l 2
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Indexing Patterns of Cubic Crystals

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Indexing Patterns of Cubic Crystals

• For the four common types, the structure

factor requires only certain combinations
– Simple Cubic: 1,2,3,4,5,6,8,9,10,11,12,13,14,…
– Body Centered Cubic: 2,4,6,8,10,12,14,16,…
– Face-centered cubic: 3,4,8,11,12,16,…
– Diamond cubic: 3,8,11,16,…
• Each set can be tried in turn.
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Example
• Using a diffraction profiles, sin2q is calculated for the first
8 diffractions
– sin2q =0.140, 0.185, 0.369, 0.503, 0.548, 0.726, 0.861, 0.905
• Values of sin2q /s is then calculated for the three cubic
systems. If the diffraction positions belong to a specific
lattice type the ratio sin2q /s should be constant!
• FCC: (s= 3, 4, 8, 11, 12, 16, 19, 20)
– sin2q / s: 0.0467, 0.0463, 0.0461, 0.0457, 0.0457, 0.0454, 0.0453, 0.0453
• Simple Cubic: (s=1, 2, 3, 4, 5, 6, 8, 9)
– sin2q / s: 0.140, 0.093, 0.123, 0.123, 0.110, 0.121, 0.108, 0.101
• BCC: (s=2,4,6,8,10,12, 14,16)
– sin2q / s: 0.070, 0.0463, 0.0615, 0.0629, 0.0548, 0.0605, 0.0615, 0.0566)
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Example

• It is obvious that only the case of FCC where

– sin2q / s: 0.0467, 0.0463, 0.0461, 0.0457, 0.0457, 0.0454, 0.0453, 0.0453

• The ratio of sin2q / s is constant. The materials is then

recognized as Face Centered Cubic
• Now the lattice parameter, a, can now be calculated from
• or , sin θ
=
sin θ
=
2
λ 2 2

(h 2
+ k2 + l2 ) s 4a2 λ λ
• For the material above a=
2sin θ
s=
2sin θ
2 2
h +k +l
2

– a= 3.57, 3.59, 3.59, 3.61, 3.61, 3.62, 3.62, 3.62

• The materials is then “Copper” with a=3.62A
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Non-cubic Crystal Systems

• In non-cubic crystals the number of

unknowns increase from one lattice
parameter to more!
• The simplest case is that of Tetragonal;
since the sin2q is calculated:
2 2 2 2
sin θ = A(h + k ) + Cl
λ2 λ2
• Where A= 2
4a
and C= 2
4c
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Indexing of Tetragonal Crystal System

• The value of A is found from the hk0 lines. When l=0, we

get: 2 2 2
sin θ = A(h + k )
• The permissible values of (h2+k2) are 1, 2, 4, 5, 8,…
• Then sin2q values of the hk0 will be in ratios of these
integers.
• C is obtained from the other lines and using
2 2 2 2
sin θ − A(h + k ) = Cl
• Which must have 1,4,9,16, …
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Indexing of Hexagonal Systems

• Similar procedure to Tetragonal except that the

sin2q values are given from
2 2 2 2
sin θ = A(h + hk + k ) + Cl
• Where: A = λ and C = λ
2

2
2

2
3a 4c
• Using Appendix 9: permissible values of h 2 + hk + k 2
1, 3, 4, 7, 9, etc.
• To show the indexing an example of Zink is used
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Indexing of Zn-Hexagonal Systems

• sin2q values is first

obtained from the
diffraction profile

– table 10.2
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Indexing of Zn-Hexagonal Systems

• First divide the sin2q values by the integers 1, 3, 4,

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Indexing of Zn-Hexagonal Systems

• Examining the numbers in Table 10-3, look for quotients

which are equal to one another or one of the observed sin2q
values.
• The two starred entries in the second and third columns
(entries 2 and 5) are the most nearly equal. Assume that
these entries are from hk0 lines.
• This means that A=0.112, which is the same as saying that
line 2 is 100
• Line 5 is then 110 (since it is nearly three times that of line
2.
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Indexing of Zn-Hexagonal Systems

• To find C, use sin 2 θ − A(h2 + k 2 ) = Cl 2

• subtract from each sin2q value the value of A(=0.112),
3A(=0.336), 4A(=0.448), etc,
• look for remainders, or (Cl2) which are nearly in the ratio
1,4,9,and 16. Numbers 0.024, 0.097, 0.221, and 0.390 are
very nearly 1, 4, 9, and 16 which gives C=0.024.
• This identifies line 1 as 002 and line 6 as 004.
• Line 3 is a sum of A and C and must be 101.
• Lines 4 and 5 are found to be 102 and 103 respectively
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Indexing of Zn-Hexagonal Systems

• Table 10.4 in C&S

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Indexing of Orthorhombic System

2 2 2 2
• The basic equation is: sin θ = Ah + Bk + Cl
• It is obvious that the indexing is much more
difficult
• The general procedure is to search for significant
differences between various pairs of sin2q values.
• For example any two lines with indices hk0 and
hk1 such as 120 and 121; the difference is C.
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Indexing of Monoclinic and Triclinic
System
• These crystal structures involve four (Monoclinic)
and six constants (Triclinic).
• The powder patterns are of great complexity and
may contain more than 100 lines.
• Computer programs may give several sets!
• The crystal structures of these low symmetry
structures are almost always determined by
examining a single crystal using a rotating crystal
method
 37

Number of atoms in a cell

• The volume of the unit cell can be calculated from
Appendix 3 and multiplied by the density of the substance
equals to the weight of all the atoms in the cell!
ρV
∑A = 1.66042 ∑A = n1 A(= n1 M)

• Where ∑ A is the sum of the atomic weights of the

atoms in the unit cell,
• r (g/cm3) is the density,
• A the atomic weight
• V is the volume of the unit cell (A3),
• n1 is number of atoms per unit cell,
• n2 is the number of molecules per unit cell
• M is the molecular weight.