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1 H 3 Li 11 Na 19 K 37 Rb 55 Cs 87 Fr
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(periodic table) ( i di t bl )
4 Be B 12 Mg g 20 Ca 38 Sr 56 Ba 88 Ra --21 Sc 39 Y 57 La 89 Ac --22 Ti 40 Zr 72 Hf 104 Rf --23 V 41 Nb 73 Ta 105 Db --24 Cr 42 Mo 74 W 106 Sg 25 Mn 43 Tc 75 Re 107 Bh 26 Fe 44 Ru 76 Os 108 Hs --27 Co 45 Rh 77 Ir 109 Mt --28 Ni 46 Pd 78 Pt 110 Uu n --29 Cu 47 Ag 79 Au 111 Uu u --30 Zn 48 Cd 80 Hg 112 Uu b 5 B 13 Al 31 Ga 49 In 81 Tl 6 C 14 Si 32 Ge 50 Sn 82 Pb 7 N 15 P 33 As 51 Sb 83 Bi 8 O 16 S 34 Se 52 Te 84 Po 9 F 17 Cl 35 Br 53 I 85 At
2 He 10 Ne N 18 Ar 36 Kr 54 Xe 86 Rn
Basic definitions
Crystal: constructed by the infinite p groups repetition of identical g p of atoms. Basis: a group of atoms. L tti Lattice: th set of mathematical points t the t f th ti l i t to which the basis is attached. An infinite array of points in space, in which each point has identical surroundings to all others.
Translational Sy a s at o a Symmetry et y
T Translationally symmetric or periodic: b i i a point l ti ll ti i di bringing i t back to an equivalent point in the crystal. yp p y g g One can reach any point in space by adding an integer number of translation vectors. If the lattice was infinite, you could not tell if you moved or not not.
Crystal structure
Lattice
+
Basis
Crystal structure
Crystal structure
Even if there is only one type of atoms in the crystal, we y yp y , have to use a basis made up with two atoms.
Lattice vectors
We need to identify the symmetry (lattice t (l tti vectors) and lattice contents (basis) to fully describe a crystal structure. How do we choose lattice vectors? (this will lead us to thinking about unit cell or primitive cell.
Unit cell
Unit cell is the basic building block of the crystal structure (it fills space). The choice of unit cell is arbitrary arbitrary. The choice of the origin for unit cells is arbitrary as well. bi ll The only requirement is that the lattice must look the same when translated by a crystal translational vector:
T = u1a1 + u1a2 + u3 a3
where u1 , u2 and u3 are integers.
Building Blocks
Different crystal faces are developed even with identical building g blocks.
Rock salt
Primitive cell
A primitive cell is a type of unit cell. A primitive cell is the parallelepiped defined by the primitive translation vectors (axes) a1 , a2 and a3 such that there is no cell of smaller volume that can be used as a building block for crystal structure. A primitive cell is a minimum-volume cell. The volume of a primitive cell is
Vc = a1 (a2 a3 )
A primitive cell will fill space by the repetition of suitable crystal translation vectors vectors.
Symmetry operations
Crystal lattice can be carried or mapped into themselves by the lattice translations T and by various other symmetry operations. Physicists use the symmetry of the unit cells to classify crystal y p structures and how they fill space. This involves the use of point group operations and translation operations. By lattice point group we mean the collection of symmetry operations which, applied about a lattice point, carry the lattice into itself. Examples: mirror reflection, inversion, n-fold rotational axis symmetry t
Penrose tiling in 2D
It turns out that one can fill space by using rotation of unit cells by 2, 2/2, 2/3, 2/4, and 2/6 radians. But rotation of 2/5, and 2/7 do not fill space. A quasicrystal is a quasi-periodic nonrandom assemble of two types of distinct designs of tiles.
Packing fraction g
a3 = z.
e.g., Po (Polonium)
One lattice point per unit cell, with a total volume of a3 Number of nearest neighbors: 6 Nearest neighbor distance: a Number of next-nearest neighbors: 12 Next-nearest neighbor distance: Packing fraction: / 6
2a a
2 lattice points per cell, with a primitive cell volume of a3/2 i iti ll l f Number of nearest neighbors: 8 Nearest neighbor distance: 3a / 2 Number of next-nearest neighbors: 6 g Next-nearest neighbor distance: a Packing fraction: 3 / 8
Wigner-Seitz cells in 3D g
http://www.chembio.uoguelph.ca/educmat/chm729/wscells/construction.htm
BCC lattice
SC lattice
Procedure: Choose any lattice site as the origin. Starting at the origin draw vectors to all neighbouring lattice points. Construct a plane p p p perpendicular to and p passing through the midpoint g g p of each vector. The area enclosed by these planes is the Wigner-Seitz cell.
The Wigner-Seitz cell may look a bit strange, but it h th f ll point t b t has the full i t symmetry of its lattice point and will be useful when we look at the reciprocal space space. movie
4 lattice points per cell, with a primitive cell volume of a3/4 Number of nearest neighbors: 12 g Nearest neighbor distance: a / 2 Number of next-nearest neighbors: 6 Next-nearest neighbor distance: a Packing fraction: 2 / 6
1 a ( x + y); 2 1 a2 = a ( y + z ) ; 2 1 a3 = a ( x + z ) . 2 a1 =
Movies
a1 = a2 a3
Index
Intercepts: a, , Reciprocals: a/a, a/, a/ = 1, 0, 0 Miller index for this plane : (1 0 0) (note: this is the normal vector for this l thi plane) )
Intercepts: a,a,a Reciprocals: a/a, a/a, a/a = 1, 1, 1 Miller index for this l Mill i d f thi plane : (1 1 1)
Intercepts: 1/2a, a, Reciprocals: 2a/a, a/a, a/ , , = 2, 1, 0 Miller index for this plane : (2 1 0)
Intercepts: 3a1, 2a2, 2a3 Reciprocals: a1/3a1, a2/2a2, a3/2a3 = 1/3, 1/2, 1/2 The smallest three integers having the same ratio: 2 3 3 h i 2, 3, Miller index for this plane : (2 3 3)
[100] direction
[001] di ti direction
The l Th plane (200) means a plane parallel t (100) b t cutting the a1 axis at a/2. l ll l to but tti th i t /2
NaCl structure
Crystal LiH MgO MnO NaCl AgBr PbS KCl KBr a () 4.08 4.20 4.43 4 43 5.63 5.77 5.92 6.29 6.59 6 59
ClNa+
movie
CsCl structure
Crystal C t l BeCu AlNi CuZn CuPd AgMg LiHg NH4Cl TlBr CsCl TlI a () 2.70 2.88 2 88 2.94 2.99 2 99 3.28 3.29 3 29 3.87 3.97 3 97 4.11 4.20 4 20
a
Why are the a values smaller for the CsCl structures than for the NaCl (in general)?
Closed-packed structures
There are an infinite number of ways to arrange identical spheres in a regular array that maximize the packing fraction.
The centers of spheres at A, B, and C positions iti
There are different ways you can pack spheres together. This y y p p g shows two ways, one by putting the spheres in an ABAB arrangement, and the other with ABCABC.
e.g., Be, Sc, Te, Co, Zn, Y, Zr, Tc, Ru, Gd, Tb, Py, Ho, Er, Tm, Lu, Hf, Re, Os, Tl
Rotate three times To get the full structure Primitive cell has a1= a2 Conventional HCP unit cell
FCC (CCP) structure has the stacking arrangement of t t h th t ki t f ABCABCABC sequence along the [111] direction.
HCP lattice
ABABAB
y x
FCC lattice ABCABCABC
ABAB sequence
ABCABC sequence
movies
Diamond structure
2 interpenetrating FCC lattices
The space lattice is FCC. The primitive basis has two identical atoms at the 000 and positions. There are 8 atoms in each conventional unit cube Number of the nearest neighbors: 4 Number of the next nearest neighbors: 12 Packing fraction: 0.34 (show this!) Crystal a () 3.567 5.430 5.658 5 658 6.49
C Si Ge G Sn
Diamond structure
FCC lattice + basis of 2 atoms at (0,0,0) and (1/4,1/4,1/4)
0 3/4 1/2 1/4 0 1/2 0 3/4 0 Tetrahedral bonding : 4 nearest neighbors 12 next nearest neighbors 1/2 1/4 1/2 0
AlAs
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1 H 3 Li 11 Na 19 K 37 Rb 55 Cs 87 Fr
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(periodic table) ( i di t bl )
4 Be B 12 Mg g 20 Ca 38 Sr 56 Ba 88 Ra --21 Sc 39 Y 57 La 89 Ac --22 Ti 40 Zr 72 Hf 104 Rf --23 V 41 Nb 73 Ta 105 Db --24 Cr 42 Mo 74 W 106 Sg 25 Mn 43 Tc 75 Re 107 Bh 26 Fe 44 Ru 76 Os 108 Hs --27 Co 45 Rh 77 Ir 109 Mt --28 Ni 46 Pd 78 Pt 110 Uu n --29 Cu 47 Ag 79 Au 111 Uu u --30 Zn 48 Cd 80 Hg 112 Uu b 5 B 13 Al 31 Ga 49 In 81 Tl 6 C 14 Si 32 Ge 50 Sn 82 Pb 7 N 15 P 33 As 51 Sb 83 Bi 8 O 16 S 34 Se 52 Te 84 Po 9 F 17 Cl 35 Br 53 I 85 At
2 He 10 Ne N 18 Ar 36 Kr 54 Xe 86 Rn
Structure Change
Many crystals undergo structural changes with T, P: For example:
-ferrite
BCC FCC
-ferrite
BCC Liquid Temperature T t 1400oC 2100oC
Fe F
910oC
BCC
FCC 371K
Liquid Temperature
Na
36K