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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.

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(C). AB Stacking AC Stacking 2 .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).

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…) 3 .

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% 4 .

Generally we will consider two types of holes (for the cations) • Octahedral holes .Eutactic Structures Many ionic structure types can be described as a close packing of anions with cations filling voids or holes in the structure.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) 5 .

6 . rutile.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. CaF2) the cations are close packed and the anions fill the tetrahedral holes.e. The opposite is true of the antifluorite structure (Na2O) hcp anion layers are buckled in 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 ½ y 0 ½ z 0 ½ Space Group = Fm3m Atom Site x Anion 4a 0 Tetr Hole 8c ¼ y 0 ¼ z 0 ¼ 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 ¼ y 0 ¼ z 0 ¼ Space Group = Fm3m Atom Site x Anion 4a 0 Tetr Hole 8c ¼ y 0 ¼ z 0 ¼ 7 .

Tetr. Coord. 50% Tetr. 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 z 0 8 . → Tetrahedron Anion Coord. ccp. Coord. Holes Filled) Sphalerite (ZnS) (hcp. 50% Tetr. Cation Coord. Coord. Holes Filled) Wurtzite (ZnO) Space Group = FF-43m Atom Site x Zn 4a 0 S 4c ¼ y 0 ¼ z 0 ¼ Space Group = P63mc Atom Site x 1/3 Zn 2b 1/3 O 2b 2/3 2/3 y 0 0.38 z Cation Coord. → Tetrahedron Connectivity → Corner sharing Oct.(ccp. → Tetrahedron Connectivity → Corner sharing Oct. Tetr. hcp. Coord. → Tetrahedron Anion Coord.

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 z X-ray Diffraction 9 .HCP Anion Array .

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 θ Divergent X-ray Source Antiscatter Slit Receiving Slit 2θ Horizontal Soller Slits Detector 10 .

Bragg’s Law 11 .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.

Determine the 2-theta value.X-ray Powder Pattern Bond Distance from XRD Pattern (Ex. 20 2θ = 38. Rock Salt Structure) 1. PbS. l=0 00 80 60 40 20 0 20 25 30 35 40 2Theta 45 50 55 60 65 Bragg’s Law: λ = 2dhkl sin θhkl 12 .7° h=2. and hkl values for a diffraction peak Int. k=2. PbS. 2θ.

541 Å /{2 sin (38. is related to the unit cell size. dhkl.541 Å) to calculate dhkl λ = 2dhkl sin θhkl dhkl = λ /(2 sin θhkl) dhkl = 1. Now that we know the unit cell size.Bond Distance from XRD (Cont. For a cubic crystal: a = (h2 + k2 + l2)1/2 dhkl a = (22 + 22 + 02)1/2(2.94 Å/2 dist (Pb-S) = 2.) (Ex. The interplanar spacing. dist (Pb-S) = a/2 dist (Pb-S) = 5.7°/2)} = 2.) (Ex. the Pb-S distance can be determined from the unit cell using simple geometry. PbS.10 Å 3. Rock Salt Structure) 2. PbS. Rock Salt Structure) 4.97 Å 13 . Use Bragg’s Law and the wavelength of radiation (typically λ = 1. PbS. PbS.10 Å) = 5.94 Å Bond Distance from XRD (Cont.

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) 14 . where h.Peak Positions Bragg’s Law: λ = 2dhkl sin θhkl The distance between different planes of atoms in a crystal. dhkl.