Determination of Crystal Structure (Chapt.

10)
Crystal Structure
Unit Cell
Atom Positions

Guess

No

Guess
Correct?
Yes

Done

Diffraction Pattern
Line Positions
Line Intensities

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 sin2 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:
2d sin K
2d sin K

4d

2K

sin2

2K

sin2

2K

sin2 sin2
2
K

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)

Cubic Crystals (Indexing the Patterns)

sin2

Line
1
2
3
4
5
6
7
8

2
4a

k2 l2 :

sin2
0.140
0.185
0.369
0.503
0.548
0.726
0.861
0.905

(h2

k2 l2

Simple cubic:
Body-centered cubic:
Face-centered cubic:
Diamond cubic:
Simple cubic
+ k2 + l2)
2
1
2
3
4
5
6
8
9

4a 2
0.140
0.093
0.123
0.126
0.110
0.121
0.108
0.101

(h2

1,
2,
3,
3,

k2
2
4
6
8
10
12
14
16

2,
4,
4,
8,

3, 4, 5, 6, 8, 9, 10, 11, 12, 13, 14, etc.

6, 8, 10, 12, 14, 16, . . .
8, 11, 12, 16, 19, 20, . . .
11, 16, 19, 24, 27, 32, . . .

bcc
+ l2)

4a 2
0.070
0.046
0.062
0.063
0.055
0.061
0.062
0.057

(h2

k2
3
4
8
11
12
16
19
20

fcc
+ l2)

2
4a 2
0.0467
0.0463
0.0461
0.0457
0.0457
0.0454
0.0453
0.0453

a()

hkl

3.57
3.59
3.59
3.61
3.61
3.62
3.62
3.62

111
200
220
311
222
400
331
420

Corrections for Systematic Errors

S
4R

ln ln S ln 4 ln R
S R

S
R

S 2ON 2x sin 2
2x sin 2 x
S

sin cos

S
4
R

Absorption error can be lumped into this error.

S R

R
S

S ,R

x
S R

sin cos

S
R
R

S ,R ,C , A

Correction for Systematic Error

Differentiation of Braggs Law:

2d sin

dd d

2 cos

d
2 sin
4 sin2

2 sin

d
cot
d

2 2d sin cos
4 sin2

For a cubic crystal:

2

a d h k l

a d

a
d

Fractional error in a
(goes to zero as 90)

Correction for Systematic Error

90 , , sin cos, cos sin

d cos
sin
sin S R
x

sin cos

d
sin
cos
cos S
R
R

At small (large ), this could be approximated as:

d
K sin2 K cos 2
d

d a a ao

K cos 2
d
a
ao
a a o a o K cos 2

Correction for Systematic Error

4
(/2 - )*cos()/sin()
3.5

100*cos

+ cos ()
2

(/2 - )*cos()/sin()

10*cos

Magnitude

2.5

1.5
2

cos
1

0.5

0.1*cos
2

0.01*cos

0
-20

20

40

60

80

100

Nelson-Riley
4

3.5

Nelson Riley
function

(/2 - )*cos()/sin()

= (cos /sin ) + (cos /)

Magnitude

2.5
2

2*cos
2

1.5
2

cos
1

0.5

0
-20

20

40

60

80

100

Indexing Patterns for Non-Cubic Crystals

Tetragonal
1
d

h2 k2
a

l2
c

2
1 2
l

2 h k2
2

a
c
a

2 log d 2 log a log h 2 k 2

l2

c 2
a

l 22
l12
2
2
2
2

2 log d1 2 log d2 log h1 k1

log h 2 k 2
2

c
c 2
a
a

Depends on (c/a), but not on a.

Dull-Harvey Chart

Indexing Patterns for Non-Cubic Crystals

Tetragonal
1
d2

h2 k2
a2

l2
c2

2
2

l
h2 k2

sin2
2
2
4a
c
a

2
2
1 2
l
4 sin
2 h k2
a
2
c 2
a

2
l2
2
2

log sin log

log h k

4a 2
c 2

log sin 1 log sin 2 log

2

h12

k12

2
l
l12
2
2

log h 2 k 2 2 2
2

c
c

a
a

Depends on (c/a), but not on a.

Scales for Left Side of Above Equations

d scale

10

sin2 scale

0.5

0.1

0.05

0.01

10

Hexagonal Hull-Davey Chart

Zinc Example (Cu K)

0.5

0.1

0.05

From table 10-2 (sin2)

0.01

0.5

0.1

0.05

0.01

10-5

0.5

0.1

0.05

0.01

0.05

0.01

10-7

0.5

0.1

10-8

Chapter 10 Example
line
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

sin
0.0462
0.1198
0.1615
0.179
0.234
0.275
0.346
0.391
0.461
0.504
0.575
0.616
0.688
0.729
0.799
0.84

sc
(h + k 2 + l2)
1
2
3
4
5
6
8
9
10
11
12
13
14
15
16
17
2

fcc
(h + k 2 + l2)
/4a
0.0462
3
0.0599
4
0.053833
8
0.04475
11
0.0468
12
0.045833
16
0.04325
19
0.043444
20
0.0461
24
0.045818
27
0.047917
32
0.047385
35
0.049143
36
0.0486
40
0.049938
43
0.049412
44
2

bcc
(h + k 2 + l2)
/4a
0.0154
2
0.02995
4
0.020188
6
0.016273
8
0.0195
10
0.017188
12
0.018211
14
0.01955
16
0.019208
18
0.018667
20
0.017969
22
0.0176
24
0.019111
26
0.018225
30
0.018581
32
0.019091
34
2

/4a
0.0231
0.02995
0.026917
0.022375
0.0234
0.022917
0.024714
0.024438
0.025611
0.0252
0.026136
0.025667
0.026462
0.0243
0.024969
0.024706

diamond
(h2 + k 2 + l2)
3
8
11
16
19
24
27
32
35
40
43
48
51
56
59

/4a
0.0154
0.014975
0.014682
0.011188
0.012316
0.011458
0.012815
0.012219
0.013171
0.0126
0.013372
0.012833
0.01349
0.013018
0.013542

Extended Hull-Davey Chart

Hull-Davey for Cubic

Hull Davey cubic

dia.
(c/a) = 1

bcc
fcc
sc
100

10

Sin2 Scale of Table 10-5

0.5

0.5

0.1

0.1

0.05

0.05

0.01

0.01

Chapter 10 Example
line
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

sin
0.0462
0.1198
0.1615
0.179
0.234
0.275
0.346
0.391
0.461
0.504
0.575
0.616
0.688
0.729
0.799
0.84

fcc
(h + k 2 + l2)
3
8
11
12
16
19
24
27
32
35
40
43
48
51
56
59
2

/4a
0.0154
0.014975
0.014682
0.014917
0.014625
0.014474
0.014417
0.014481
0.014406
0.0144
0.014375
0.014326
0.014333
0.014294
0.014268
0.014237