Determination of Crystal Structure (Chapt.

10)
Crystal Structure Diffraction Pattern
Unit Cell Line Positions
Atom Positions Line Intensities
Guess
Guess
Correct?
Done
Yes
No
1. Use the angular positions of the diffraction lines to determine
the shape and size of the unit cell.
Assume either cubic, tetragonal, orthorhombic,
rhombohedral, hexagonal, monoclinic, or triclinic.
Assign Miller indices to each reflection (index the
pattern).
If a match is not obtained, the assumption of should be
changed and the pattern indexed again.
Calculate the size of the unit cell based on the positions
and Miller indices of the diffraction lines.
2. With the measured density of the material, the chemical
composition, and the size of the unit cell, calculate the
number of atoms per unit cell.
3. Find the positions of the atoms in the unit cell by using the
relative intensities of the diffraction lines.
Preliminary Treatment of Data
We want the values of sin
2
u for each diffraction line (in order to find the cell size and
shape), however, there can be errors to what we measure, including extraneous
lines in the diffraction pattern, and systematic errors (misalignment, film
shrinkage, absorption, etc.)

Extraneous Lines
1. X-ray beam with multiple wavelengths:





2. Contaminants or impurities in the sample, or the specimen mount!

Systematic Errors
1. Film shrinkage (see Fig. 6-5 Cullity)
2. Specimen is off-centered in Debye-Scherrer camera (see Fig. 11-3 Cullity)
3. Absorption in the sample

Answer mix in a reference material and calibrate. (see Fig. 10-1 Cullity)
|
o
= u
= u
|
o
K
K
d
d
sin 2
sin 2
| o
u

=
u

=
|
o
2
2
2
2
2
sin sin
4
K
K
d
o |
u = u
|
|
.
|

\
|

|
o 2 2
2
2
sin sin
K
K
Cubic Crystals (Indexing the Patterns)
( )
2 2 2
2
2
2
4
sin l k h
a
+ +

= u
( ):
2 2 2
l k h + + Simple cubic: 1, 2, 3, 4, 5, 6, 8, 9, 10, 11, 12, 13, 14, etc.
Body-centered cubic: 2, 4, 6, 8, 10, 12, 14, 16, . . .
Face-centered cubic: 3, 4, 8, 11, 12, 16, 19, 20, . . .
Diamond cubic: 3, 8, 11, 16, 19, 24, 27, 32, . . .
Simple cubic bcc fcc
Line sin
2
u (h
2
+ k
2
+ l
2
)
2
2
4a

(h
2
+ k
2
+ l
2
)
2
2
4a

(h
2
+ k
2
+ l
2
)
2
2
4a

a() hkl
1 0.140 1 0.140 2 0.070 3 0.0467 3.57 111
2 0.185 2 0.093 4 0.046 4 0.0463 3.59 200
3 0.369 3 0.123 6 0.062 8 0.0461 3.59 220
4 0.503 4 0.126 8 0.063 11 0.0457 3.61 311
5 0.548 5 0.110 10 0.055 12 0.0457 3.61 222
6 0.726 6 0.121 12 0.061 16 0.0454 3.62 400
7 0.861 8 0.108 14 0.062 19 0.0453 3.62 331
8 0.905 9 0.101 16 0.057 20 0.0453 3.62 420
Corrections for Systematic Errors
R
S
4
'
= |
R
R
S
S
R S
A

'
' A
=
|
| A
' = | ln 4 ln ln ln
|
|
.
|

\
| A

'
' A
= | A
'
R
R
S
S
R S ,
| A = = ' A 2 sin 2 2 x ON S
| |
A
=
|
| A |
= |
|
.
|

\
|
'
' A
= | A cos sin
4
2 sin 2
R
x
R
x
S
S
C
Absorption error can be lumped into this error.
| |
A
+ |
|
.
|

\
| A

'
' A
= | A
'
cos sin
, , ,
R
x
R
R
S
S
A C R S
Correction for Systematic Error
For a cubic crystal:
Differentiation of Braggs Law:
= u sin 2d
u

=
sin 2
d
( )
u
u u
=
u
u
=
u

=
u A
A
=
u
2
2
sin 4
cos sin 2 2
sin 4
cos 2
sin 2
d
d
d
dd
u u A =
A
cot
d
d
2 2 2
l k h d a + + =
d
d
a
a A
=
A
Fractional error in a
(goes to zero as u 90)
Correction for Systematic Error
u = | u = | u A = | A u = | sin cos , cos sin , , 90

| |
A
+ |
|
.
|

\
| A

'
' A
|
|
= | A
|
|
= u A
u
u
=
A
cos sin
cos
sin
cos
sin
sin
cos
R
x
R
R
S
S
d
d
At small | (large u), this could be approximated as:
u = | =
A
2 2
cos sin K K
d
d
u =

=
A
=
A
2
cos K
a
a a
a
a
d
d
o
o
u + =
2
cos K a a a
o o
Correction for Systematic Error
0
0.5
1
1.5
2
2.5
3
3.5
4
-20 0 20 40 60 80 100
M
a
g
n
i
t
u
d
e
u
0.01*cos
2
u
cos
2
u
(t/2 - u)*cos(u)/sin(u)
0.1*cos
2
u
10*cos
2
u
100*cos
2
u
(t/2 - u)*cos(u)/sin(u)
+ cos
2
(u)
Nelson-Riley
0
0.5
1
1.5
2
2.5
3
3.5
4
-20 0 20 40 60 80 100
M
a
g
n
i
t
u
d
e
u
Nelson Riley
function
2*cos
2
u
cos
2
u
= (cos
2
u/sin
2
u) + (cos
2
u/u)
(t/2 - u)*cos(u)/sin(u)
Indexing Patterns for Non-Cubic Crystals
Tetragonal
( )
( )
(
(
(

+ + = +
+
=
2
2
2 2
2 2
2
2
2 2
2
1 1
a
c
l
k h
a c
l
a
k h
d
( )
( )
(
(
(

+ + + =
2
2
2 2
log log 2 log 2
a
c
l
k h a d
( )
( )
( )
( )
(
(
(

+ + +
(
(
(

+ + =
2
2
2 2
2
2
2
2
2
1
2
1
2
1 2 1
log log log 2 log 2
a
c
l
k h
a
c
l
k h d d
Depends on (c/a), but not on a.
Dull-Harvey Chart
Indexing Patterns for Non-Cubic Crystals
Tetragonal
( )
( )
2
2
2
2
2 2
2 2
2
2
2 2
2
sin 4 1 1

u
=
(
(
(

+ + = +
+
=
a
c
l
k h
a c
l
a
k h
d
( )
( )
(
(
(

+ + +

= u
2
2
2 2
2
2
2
log
4
log sin log
a
c
l
k h
a
( )
( )
( )
( )
(
(
(

+ +
(
(
(

+ + = u u
2
2
2 2
2
2
2
2
2
1
2
1
2
1 2
2
1
2
log log sin log sin log
a
c
l
k h
a
c
l
k h
Depends on (c/a), but not on a.
( )
( )
(
(
(

+ +

= u
2
2
2 2
2
2
2
4
sin
a
c
l
k h
a
Scales for Left Side of Above Equations
1 10 2 3 4 6 5 7 8 9
0.01 0.1 1 0.5 0.05
d scale
sin
2
u scale
1 10 2 3 4 6 5 7 8 9
Hexagonal Hull-Davey Chart
Zinc Example (Cu K
o
)
From table 10-2 (sin
2
u)
0.01 0.1 1 0.5 0.05
0.01 0.1 1 0.5 0.05
10-7
0.01 0.1 1 0.5 0.05
10-5
0.01 0.1 1 0.5 0.05
10-8
Chapter 10 Example
sc fcc bcc diamond
line sin
2
u (h
2
+ k
2
+ l
2
)
2
/4a
2
(h
2
+ k
2
+ l
2
)
2
/4a
2
(h
2
+ k
2
+ l
2
)
2
/4a
2
(h
2
+ k
2
+ l
2
)
2
/4a
2
1 0.0462 1 0.0462 3 0.0154 2 0.0231 3 0.0154
2 0.1198 2 0.0599 4 0.02995 4 0.02995 8 0.014975
3 0.1615 3 0.053833 8 0.020188 6 0.026917 11 0.014682
4 0.179 4 0.04475 11 0.016273 8 0.022375 16 0.011188
5 0.234 5 0.0468 12 0.0195 10 0.0234 19 0.012316
6 0.275 6 0.045833 16 0.017188 12 0.022917 24 0.011458
7 0.346 8 0.04325 19 0.018211 14 0.024714 27 0.012815
8 0.391 9 0.043444 20 0.01955 16 0.024438 32 0.012219
9 0.461 10 0.0461 24 0.019208 18 0.025611 35 0.013171
10 0.504 11 0.045818 27 0.018667 20 0.0252 40 0.0126
11 0.575 12 0.047917 32 0.017969 22 0.026136 43 0.013372
12 0.616 13 0.047385 35 0.0176 24 0.025667 48 0.012833
13 0.688 14 0.049143 36 0.019111 26 0.026462 51 0.01349
14 0.729 15 0.0486 40 0.018225 30 0.0243 56 0.013018
15 0.799 16 0.049938 43 0.018581 32 0.024969 59 0.013542
16 0.84 17 0.049412 44 0.019091 34 0.024706
Extended Hull-Davey Chart
Hull-Davey for Cubic
1 10 100
Hull Davey cubic
(
c
/
a
)

=

1
dia.
bcc
dia.
fcc
dia.
sc
Sin
2
u Scale of Table 10-5
0.01 0.1 1 0.5 0.05
0.01 0.1 1 0.5 0.05
Chapter 10 Example
fcc
line sin
2
u (h
2
+ k
2
+ l
2
)
2
/4a
2
1 0.0462 3 0.0154
2 0.1198 8 0.014975
3 0.1615 11 0.014682
4 0.179 12 0.014917
5 0.234 16 0.014625
6 0.275 19 0.014474
7 0.346 24 0.014417
8 0.391 27 0.014481
9 0.461 32 0.014406
10 0.504 35 0.0144
11 0.575 40 0.014375
12 0.616 43 0.014326
13 0.688 48 0.014333
14 0.729 51 0.014294
15 0.799 56 0.014268
16 0.84 59 0.014237