Determination of Crystal Structure (Chapt.

10)
Crystal Structure Diffraction Pattern
Unit Cell Line Positions
Atom 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,
Guess 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.
Guess
Calculate the size of the unit cell based on the positions
No Correct?
and Miller indices of the diffraction lines.
2. With the measured density of the material, the chemical
Yes
composition, and the size of the unit cell, calculate the
Done 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 2K 2K 2K
2
sin2 sin2
4d 2
2d sin K sin2 sin2 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)

2
sin2
4a 2
h 2
k2 l2

h 2
k2 l2 : 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 sin2 (h2 + k2 + l2) 2 (h2 + k2 + l2) 2 (h2 + k2 + l2) 2 a() hkl
4a 2 4a 2 4a 2
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

S

4R S 2ON 2x sin 2

ln ln S ln 4 ln R S 2x sin 2 x
C sin cos
S 4R R
S R

S R
Absorption error can be lumped into this error.
S R
S ,R
S R
S R x
S ,R ,C , A sin cos
S R R
 Correction for Systematic Error

Differentiation of Braggs Law: 2d sin

d
2 sin

dd d 2 cos
d
d 2 sin 4 sin2 cot
d
2 2d sin cos

4 sin2

For a cubic crystal:

a d
2 2 2 Fractional error in a
a d h k l a d (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 d a a ao
K sin2 K cos 2 K cos 2
d d a ao

a a o a o K cos 2
 Correction for Systematic Error

(/2 - )*cos()/sin() 2
100*cos
3.5 2
+ cos ()
2
(/2 - )*cos()/sin() 10*cos
3

2.5
Magnitude

1.5

2
cos
1

0.5 2
0.1*cos
2
0.01*cos
0

-20 0 20 40 60 80 100

 Nelson-Riley
4

2 2 2
Nelson Riley = (cos /sin ) + (cos /)
3.5 (/2 - )*cos()/sin() function

2.5
2
2*cos
Magnitude

1.5

2
cos
1

0.5

-20 0 20 40 60 80 100

 Indexing Patterns for Non-Cubic Crystals

Tetragonal

2
h2 k2 l2 l2
1

1 2
2 h k2 l
2 log d 2 log a log h 2 k 2
d 2
a 2
c 2
a

c 2
a



c 2
a

2 2
2 log d1 2 log d2 log h1 k1 l12
2 2
log h 2 k 2 l 22



c 2
a


c 2
a

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

Dull-Harvey Chart
 Indexing Patterns for Non-Cubic Crystals

Tetragonal

2 2 2
h2 k2 l2

2
1

1 2
2 h k2
l
4 sin sin2
h2 k2 l
d2 a2 c2 a

c 2
a
2 4a 2

c
2
a

2 l2
2
log sin log
log h k 2 2

4a 2

c 2
a

2
log sin 1 log sin 2 log
2 2

h12 k12
l12
2

2 l
log h 2 k 2 2 2


c
2
a


c
a

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

Scales for Left Side of Above Equations

d scale

1 2 3 4 5 6 7 8 9 10

sin2 scale

1 0.5 0.1 0.05 0.01

1 2 3 4 5 6 7 8 9 10
Hexagonal Hull-Davey Chart
 Zinc Example (Cu K)

1 0.5 0.1 0.05 0.01

From table 10-2 (sin2)

1 0.5 0.1 0.05 0.01

10-5

1 0.5 0.1 0.05 0.01

10-7

1 0.5 0.1 0.05 0.01

10-8
 Chapter 10 Example

sc fcc bcc diamond

2
line sin (h + k 2 + l2)
2 2 2
/4a (h + k 2 + l2)
2 2 2
/4a (h + k 2 + l2)
2 2 2
/4a (h2 + k 2 + l2) 2 2
/4a
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

Hull Davey cubic

dia.
bcc
(c/a) = 1

fcc

sc

100 10 1
 Sin2 Scale of Table 10-5

1 0.5 0.1 0.05 0.01

1 0.5 0.1 0.05 0.01

Chapter 10 Example

fcc
2
line sin (h + k 2 + l2)
2 2 2
/4a
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