Professional Documents
Culture Documents
Determining Crystal Structure
Determining Crystal Structure
Determining Crystal Structure
10)
Crystal Structure Diffraction Pattern
Unit Cell Line Positions
Atom Positions Line Intensities
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
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, . . .
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
dd d 2 cos
d
d 2 sin 4 sin2 cot
d
2 2d sin cos
4 sin2
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
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
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
d scale
1 2 3 4 5 6 7 8 9 10
sin2 scale
1 2 3 4 5 6 7 8 9 10
Hexagonal Hull-Davey Chart
Zinc Example (Cu K)
10-5
10-7
10-8
Chapter 10 Example
dia.
bcc
(c/a) = 1
fcc
sc
100 10 1
Sin2 Scale of Table 10-5
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