Structures of Solids & X-ray Diffraction

Chemistry 123 Dr. Patrick Woodward Supplemental Lecture 4

Crystalline Solids

CaF2 Unit Cell Crystal Lattice A 3D array of points where each point has an identical environment. Unit Cell The repeating unit (a unit cell is to a crystal, like a brick brick is in a house). In a given crystal all unit cells are identical.

Cubic Tetragonal Hexagonal Rhombohedral Orthorhombic Monoclinic Triclinic

The crystal systems each have distinctive symmetry and unit cell dimensions

Crystal Systems

Close Packed Array of Spheres

The gray spheres represent a 2D Close Packed Array. In 3D the next layer of spheres could sit on the depressions marked in red (B) or those marked in blue (C). (C).

AB Stacking

AC Stacking

Cubic and Hexagonal Close Packing

Hexagonal Close Packing (ABAB (ABAB)

ABAB Stacking

Cubic Close Packing (ABCABC (ABCABC) ABCABC Stacking

Close Packed Spheres

Hexagonal Close Packing (ABAB (ABAB)

Cubic Close Packing (ABCABC (ABCABC)

Hexagonal Close Packing

Cubic Close Packing

Body Centered Cubic Packing

CsCl Structure

Cubic or Hexagonal Close Packing Coordination Number = 12 Packing Efficiency = 74% Body Centered Cubic Packing Coordination Number = 8 Packing Efficiency = 68%

Eutactic Structures
Many ionic structure types can be described as a close packing of anions with cations filling voids or holes in the structure. Generally we will consider two types of holes (for the cations)
Octahedral holes - Voids are surrounded by 6 anions and lead to octahedral coordination of the cation Tetrahedral holes - Voids are surrounded by 4 anions and lead to tetrahedral coordination of the cation

Octahedral Holes
Start with a close packed layer of anions (A)

Insert cations in the triangular depressions (c)

The resulting cation coordination is an octahedron Add another anion layer (B)

Tetrahedral Holes
Start with a close packed layer of anions (A)

Insert cations in the triangular depressions (b)

The resulting cation coordination is a tetrahedron Add another anion layer (B)

Eutactic Structures
Structures obtained by filling Octahedral Holes
Structure NaCl NiAs CdCl2 CdI2 TiO2 Al2O3
The

Structures obtained by filling Tetrahedral Holes

Structure Fluorite Sphalerite Wurtzite
In

Fraction Packing Holes Filled 1 1 1/2 1/2 1/2 2/3 ccp hcp ccp hcp hcp hcp

Fraction Packing Holes Filled 1 1/2 1/2 ccp ccp hcp

fluorite (i.e. CaF2) the cations are close packed and the anions fill the tetrahedral holes. The opposite is true of the antifluorite structure (Na2O)

hcp anion layers are buckled in rutile. rutile.

Cubic close packed (CCP) anion array

Rock salt structure (NaCl ) (NaCl) (Octahedral Holes) Antifluorite structure (Na2O) (Tetrahedral Holes)

Space Group = Fm3m Atom Site x Anion 4a 0 Oct Hole 4b

y 0

z 0

Space Group = Fm3m Atom Site x Anion 4a 0 Tetr Hole 8c

y 0

z 0

CCP Anion Array & Tetrahedral Holes

Zinc Blende Structure (ZnS ) (ZnS) (50% Tetrahedral Holes) Antifluorite structure (Na2O) (100% Tetrahedral Holes)

Space Group = F43m Atom Site x Anion 4a 0 Tetr Hole 4b

y 0

z 0

Space Group = Fm3m Atom Site x Anion 4a 0 Tetr Hole 8c

y 0

z 0

(ccp, ccp, 50% Tetr. Tetr. Holes Filled)

Sphalerite (ZnS)

(hcp, hcp, 50% Tetr. Tetr. Holes Filled)

Wurtzite (ZnO)

Space Group = FF-43m Atom Site x Zn 4a 0 S 4c

y 0

z 0

Space Group = P63mc Atom Site x 1/3 Zn 2b 1/3 O 2b

2/3 2/3

0 0.38

Cation Coord. Coord. Tetrahedron Anion Coord. Coord. Tetrahedron Connectivity Corner sharing Oct.

Cation Coord. Coord. Tetrahedron Anion Coord. Coord. Tetrahedron Connectivity Corner sharing Oct.

Hexagonal Close Packed Anion Array Nickel Arsenide Structure (Octahedral Holes)

Space Group = P63/mmc Atom Site x y 1/3 2/3 Anion 2c Oct Hole 2a 0 0

1/4

HCP Anion Array - Tetrahedral Holes No such structure exists

Space Group = P63/mmc Atom Site x y 1/3 2/3 Anion 2c Tetr Hole 4f 1/3 2/3

z ~ 0.632

1/4 z

X-ray Diffraction

Diffraction Demo
Take home message
The diffraction pattern is related but not equal to the grid pattern Diffraction is most effective for monochromatic light whose wavelength is similar to the spacing of slits slits For crystals XX-rays have a wavelength comparable to spacings of atoms

Powder Diffractometer
Horizontal Diffraction Circle Sample (Vertical Flat Plate) Divergence Slit

Divergent X-ray Source

Antiscatter Slit Receiving Slit

2
Horizontal Soller Slits Detector

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Single Crystal Diffraction

Diffracted Beam

Powder Diffraction
Diffracted Beam

Incident Beam

Incident Beam In powder diffraction only a small fraction of the crystals (shown in blue) are correctly oriented to diffract.

Braggs Law

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X-ray Powder Pattern

Bond Distance from XRD Pattern

(Ex. PbS, PbS, Rock Salt Structure)
1. Determine the 2-theta value, 2, and hkl values for a diffraction peak
Int. 20

2 = 38.7 h=2, k=2, l=0

00

80

60

40

20

0 20 25 30 35 40 2Theta 45 50 55 60 65

Braggs Law:

= 2dhkl sin hkl

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Bond Distance from XRD (Cont.)

(Ex. PbS, PbS, Rock Salt Structure)
2. Use Braggs Law and the wavelength of radiation (typically = 1.541 ) to calculate dhkl

= 2dhkl sin hkl dhkl = /(2 sin hkl) dhkl = 1.541 /{2 sin (38.7/2)} = 2.10
3. The interplanar spacing, dhkl, is related to the unit cell size. For a cubic crystal:

a = (h2 + k2 + l2)1/2 dhkl a = (22 + 22 + 02)1/2(2.10 ) = 5.94

Bond Distance from XRD (Cont.)

(Ex. PbS, PbS, Rock Salt Structure)
4. Now that we know the unit cell size, the Pb-S distance can be determined from the unit cell using simple geometry.

dist (Pb-S) = a/2 dist (Pb-S) = 5.94 /2 dist (Pb-S) = 2.97

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Peak Positions
Braggs Law:

= 2dhkl sin hkl

The distance between different planes of atoms in a crystal, dhkl, where h, k and l are integers that correspond to different planes

Cubic: 1/d2 = (h2 + k2 + l2)/a2 Tetragonal: 1/d2 = {(h2 + k2)/a2} + (l2/c2) Orthorhombic: 1/d2 = (h2/a2) + (k2/b2) + (l2/c2) Hexagonal: 1/d2 = (4/3){(h2 + hk + k2)/a2} + (l2/c2)

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