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)

110 10 0.61 222 6 0. 16. 10. Body-centered cubic: 2. 24.063 11 0.061 16 0.0454 3.0453 3.59 200 3 0.108 14 0.62 420 . 12. 19. 19.0467 3.070 3 0. etc. Face-centered cubic: 3.126 8 0.369 3 0. 4. 8. .905 9 0. .062 8 0. Cubic Crystals (Indexing the Patterns) 2 sin2   4a 2 h 2  k2  l2  h 2  k2  l2 :  Simple cubic: 1. Diamond cubic: 3. 6. Simple cubic bcc fcc Line sin2 (h2 + k2 + l2) 2 (h2 + k2 + l2) 2 (h2 + k2 + l2) 2 a(Å) hkl 4a 2 4a 2 4a 2 1 0. 32. . 8.140 1 0. 11. 14. 2.185 2 0. 8. 27.726 6 0.503 4 0.046 4 0.861 8 0. 16. 14.055 12 0. 20. 4. 5.57 111 2 0. 3.101 16 0. 9.59 220 4 0.093 4 0.61 311 5 0. 4.62 400 7 0.0453 3. 12. 11.121 12 0.0463 3. 10. . . . 6. 12. .062 19 0.548 5 0. .62 331 8 0.057 20 0.0461 3. 13. 16. 8.0457 3. 11. .123 6 0.140 2 0.0457 3.

Corrections for Systematic Errors S  4R S   2ON  2x sin 2 ln   ln S   ln 4  ln R  S   2x sin 2 x C     sin  cos   S   4R  R  S  R    S R Absorption error can be lumped into this error.R .  S  R  S .R      S R   S  R  x S .C . A      sin  cos   S  R  R .

Correction for Systematic Error Differentiation of Bragg’s 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) .

   . 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  . sin  cos. Correction for Systematic Error   90   . cos  sin d  cos  sin  sin    S  R  x            sin  cos  d sin  cos  cos    S  R  R  At small  (large ).

01*cos  0 -20 0 20 40 60 80 100  .5 Magnitude 2 1. Correction for Systematic Error 4 (/2 .1*cos  2 0.5 2 + cos () 2 (/2 .)*cos()/sin() 2 100*cos  3.5 2 0.5 2 cos  1 0.)*cos()/sin() 10*cos  3 2.

5 0 -20 0 20 40 60 80 100  .5 (/2 . Nelson-Riley 4 2 2 2 Nelson Riley = (cos /sin ) + (cos /) 3.5 2 2*cos  Magnitude 2 1.)*cos()/sin() function 3 2.5 2 cos  1 0.

but not on a. . 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).

Dull-Harvey Chart .

but not on a. . 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).

1 0.01 1 2 3 4 5 6 7 8 9 10 .05 0.5 0.Scales for Left Side of Above Equations d scale 1 2 3 4 5 6 7 8 9 10 sin2 scale 1 0.

Hexagonal Hull-Davey Chart .

5 0.1 0. Zinc Example (Cu K) 1 0.01 From table 10-2 (sin2) .05 0.

1 0.1 0.5 0.01 10-8 .1 0.01 10-7 1 0.5 0.05 0.01 10-5 1 0.1 0.05 0.5 0.05 0.

575 12 0.022917 24 0.049143 36 0.616 13 0.018211 14 0.045818 27 0.012833 13 0.0231 3 0.011188 5 0.024438 32 0.011458 7 0. 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 0.0126 11 0.0176 24 0.026917 11 0.019208 18 0.025667 48 0.013372 12 0.0599 4 0.012815 8 0.04475 11 0.0243 56 0.0195 10 0.688 14 0.0468 12 0.047917 32 0.799 16 0.01955 16 0.391 9 0.019111 26 0.013018 15 0.234 5 0.0154 2 0.020188 6 0.053833 8 0.014975 3 0.024714 27 0.84 17 0.024969 59 0.1615 3 0.0461 24 0.012316 6 0.0462 3 0.017188 12 0.012219 9 0.0154 2 0.026462 51 0.729 15 0.02995 8 0.024706 .275 6 0.019091 34 0.025611 35 0.018581 32 0.0234 19 0.346 8 0.179 4 0.043444 20 0.04325 19 0.047385 35 0.01349 14 0.018225 30 0.02995 4 0.049938 43 0.014682 4 0.461 10 0.0486 40 0.026136 43 0.1198 2 0.018667 20 0.504 11 0.049412 44 0.045833 16 0.022375 16 0.016273 8 0.017969 22 0.0462 1 0.013542 16 0.0252 40 0.013171 10 0.

Extended Hull-Davey Chart .

bcc (c/a) = 1 fcc sc 100 10 1 . Hull-Davey for Cubic Hull Davey cubic dia.

05 0.01 .01 1 0.5 0.05 0.1 0. Sin2 Scale of Table 10-5 1 0.5 0.1 0.

799 56 0.014481 9 0.616 43 0.014417 8 0.014326 13 0.84 59 0.575 40 0.014975 3 0.0154 2 0.1615 11 0.461 32 0.014625 6 0.014294 15 0.014682 4 0.275 19 0.014474 7 0.014333 14 0.014268 16 0.Chapter 10 Example fcc 2 line sin  (h + k 2 + l2) 2 2 2  /4a 1 0.391 27 0.234 16 0.0462 3 0.014917 5 0.014375 12 0.1198 8 0.179 12 0.688 48 0.014237 .014406 10 0.0144 11 0.504 35 0.729 51 0.346 24 0.