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Crystals
Lattices, Planes, and Indices
solids have long range order; easily studied because of this

5.00 nm 1.0 nm

0.5 nm
2.50 mica
0.0 nm

0
0 2.50 5.00 nm
rhinovirus KAl2(AlSi3O10)(F, OH)2
(e– microscope) (atomic force microscope)

M. C. Escher
Horsemen
1946

Unit Cells 7 Crystal Systems

triclinic tetragonal
a ≠ b ≠ c a = b ≠ c
glucose  ≠  ≠   =  =  = 90o
Anders Ångstrom
Swedish monoclinic rhombohedral
(1814 - 1874) a ≠ b ≠ c a = b = c
~10–10 m = 1 Å  =  = 90o;  ≠ 90o  =  =  ≠ 90o
defined by: c
 orthorhombic cubic
3 edges; a, b, c  a a ≠ b ≠ c a = b = c
3 angles; α, β, γ   =  =  = 90o  =  =  = 90o
b
find highest possible symmetry: hexagonal solid objects that can fill space
a = b ≠ c
unit cells named after symmetry  =  = 90 ;  = 120o
o

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7 Crystal Systems Volume of Unit Cell

triclinic tetragonal
no rotational 4-fold axis along c
symmetry c face is a square

monoclinic rhombohedral
2-fold axis along b 3-fold axis along V = abc(1 – cos2– cos2– cos2 + 2 coscoscos)1/2
 > 90o one body diagonal
if , , and  is 90o (orthorhombic, tetragonal, cubic), cos = 0
orthorhombic cubic
3 perpendicular 4-fold axis along V = abc
2-fold axes a, b, and c
3-fold axes along
hexagonal all body diagonals
6-fold axis along c many 2-fold axes
2-fold axes perpendicular to c

Centered Cells 14 Bravais Lattices

triclinic monoclinic
Auguste Bravais
French P1 symmetry symbol P2/m C2/m
(1811-1863)
orthorhombic
type of centering given by symbols:
Pmmm Cmmm Immm Fmmm
P no centering; primitive
A, B, C centered on both faces ┴ to a, b or c rhombohedral tetragonal
I body-centered; in exact center of cell R3m P4/mmm I4/mmm
(Ger: innenzentriertes; interior centered)
F face-centered; centered on the 6 faces hexagonal cubic
R rhombohedral primitive
P6/mmm Pm3m Im3m Fm3m
ways in which objects can pack in crystal box to fill space

Centering Conventions Centering Conventions

no B-centering in monoclinic:
no body-centering (I) in monoclinic: B centering
C centering

can be described as primitive, but still monoclinic

still monoclinic A-centering identical with C
convention

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Centering Conventions Centered Hexagonal versus Primitive Trigonal

triple primitive hexagonal, Rhex:

no face-centering (F) in monoclinic:
primitive rhombohedral (trigonal), R

C centered monoclinic

Unit Cells Lattice Points in Unit Cells

repeating object, including additional symmetry, is the motif
1/8

1/2 1
1 1 2
corner shares 8 cells face shares 2 cells body not shared
motif may be whole molecule or several molecules
motif + lattice points = crystal structure P F I
unit cell contains whole motif or parts of several to give whole
asymmetric unit: smallest part of motif that generates crystal 8 x 1/8 8 x 1/8 + 6 x 1/2 8 x 1/8 + 1 x 1
1 lattice point 4 lattice points 2 lattice points
structure with additional symmetry
number of molecules (motifs) inside unit cell: Z
1 1 2
number of lattice points in unit cell related to volume of
alternate settings, which is related to Z 1 lp 1 lp 2 lp

Lattice Points/Volume Relationship Useful Relationship

Z(FW)
ρ =
0.60226 V

For a given array of objects: ρ density; g/cm3 (Mg/m3)

Z integer number of molecules in unit cell
VC = 2VP FW formula weight of molecule
VI = 2VP V volume; Å3

VF = 4VP 0.60226 = NA and conversion of cm3 to Å3

0.60226 V ρ 0.60226 V ρ
Z = ; FW =
FW Z

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Fractional Coordinates Distance Between Points

unit cell is used as a coordinate system
location of contents of unit cell (atoms) given as (x, y, z):
x: fraction along a y: fraction along b z: fraction along c
(0.5, 0.5, 0.5) or (½, ½, ½) point in center of unit cell
can also be – (in previous UC) or >1 (in next UC)
bond lengths (and bond angles) determined by calculating
the distance between points (atoms) in unit cell.
distance (d) between two points (x1, y1, z1) and (x2, y2, z2):

d = (x2a2 + y2b2 + z2c2 +

2x y ab cos + 2y z bc cos + 2x z ac cos)1/2

x = (x1 – x2)
y = (y1 – y2)
z = (z1 – z2)

Example Example
x = (0.0000 – (–0.0520)) = 0.0520
y = (0.5000 – 0.5347) = –0.0347
a 12.773 Å  110.43o z = (0.5000 – 0.3437) = 0.1563
b 15.326 Å  100.67o
d = (x2a2+ y2b2+ z2c2
+
c 11.641 Å  66.62o
2x y ab cos + 2y z bc cos + 2x z ac cos)1/2
d = ((0.0520)2(12.773)2 +
N3
Cu Cu (0.0000, 0.5000, 0.5000) (–0.0347)2(15.326)2 +
a
c N3 (–0.0520, 0.5347, 0.3437) (0.1563)2(11.641)2 +
b 2(0.0520)(–0.0347)(12.773) (15.326) cos(66.62o) +
x = (0.0000 – (–0.0520)) = 0.0520
2(–0.0347)(0.1563) (15.326) (11.641) cos(110.43o) +
y = (0.5000 – 0.5347) = –0.0347 2(0.0520)(0.1563) (12.773) (11.641) cos(100.67o))1/2
z = (0.5000 – 0.3437) = 0.1563
= 1.996 Å

Planes

in 2-D, a set of parallel lines (planes in 3-D) can be constructed

such that every lattice point is on some member of the set

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Planes

in 2-D, a set of parallel lines (planes in 3-D) can be constructed

such that every lattice point is on some member of the set
it follows from the repeating nature of the lattice, when a line
(or plane) cuts an axis, it always divides it into an integral
number of parts
2

2 4

4 3

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5
3

5 2
3

Planes

in 2-D, a set of parallel lines (planes in 3-D) can be constructed

such that every lattice point is on some member of the set
it follows from the repeating nature of the lattice, when a line
2 (or plane) cuts an axis, it always divides it into an integral
number of parts
3
lines (planes) generated are named, or indexed, by taking the
reciprocal of the fractional intercept, or the number of parts on
each axis; uniquely characterizes the line (plane)

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Indices Indices

x y x y
y ( 1/2 1 ) y (–1/2 –1)
cuts y at 1

cuts x at –1/2
x x
(0, 0)cuts x at +1/2 (2 1) (0, 0) (2 1)
set of
orlines (planes)
number same as ( 2 1 )
of parts cuts y at –1

Indices Indices

x y x y
y ( 1 1/2 ) y ( 1/3 1/2 )
cuts y at +1/2 cuts y at +1/2

x x
(0, 0) cuts x at +1 (1 2) (0, 0) cuts x at +1/3 (3 2)

Indices Planes

in 2-D, a set of parallel lines (planes in 3-D) can be constructed

x y such that every lattice point is on some member of the set
y ( 1/3 –1/2 ) it follows from the repeating nature of the lattice, when a line
(or plane) cuts an axis, it always divides it into an integral
number of parts
x
(0, 0) cuts x at +1/3 (3 2) lines (planes) generated are named, or indexed, by taking the
reciprocal of the fractional intercept, or the number of parts on
cuts y at –1/2
each axis; uniquely characterizes the line (plane)
Miller Planes/Miller Indices
William Hallowes Miller
British
(1801-1880)

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Miller Planes Miller Planes

z z
y y
1/2

x 1/2 x
(0, 0, 0) (0, 0, 0)

( 1/2 1/2 1 ) (2 2 1) (1 1 1) (1 1 1)

Miller Planes Miller Planes

z z

x (0, 0, 0) x (0, 0, 0)

y y

(1 1 1) (1 1 1) ( 1 1 –1 ) (1 1 1)

Miller Planes Miller Planes

z z

x (0, 0, 0) x (0, 0, 0)

y y
an index of 0 when axis not cut (1/∞)
( 1 1/2 1/2 ) (1 2 2) (1 ∞ ∞) (1 0 0)
two faces of the unit cell ( 1 0 0 )

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Miller Planes Miller Planes

z z

x (0, 0, 0) x (0, 0, 0)

y y
an index of 0 when axis not cut (1/∞) an index of 0 when axis not cut (1/∞)
(∞ 1 ∞) (0 1 0) (∞ ∞ 1) (0 0 1)
two faces of the unit cell ( 0 1 0 ) two faces of the unit cell ( 0 0 1 )

Miller Planes Miller Planes

z z

x (0, 0, 0) x (0, 0, 0)

y y
an index of 0 when axis not cut (1/∞) indices of parallel planes in-between are multiples of smallest.
(1 1 ∞) (1 1 0) ( 1/2 ∞ ∞ ) (2 0 0)

Miller Planes Miller Planes

note: do not intersect lattice points in classical crystallography planes that are multiples,
(1 0 0) (2 0 0) (3 0 0)
z
are the same; referred to external faces of a crystal

(1 1 1) (1 0 1) (0 1 1)
x (0, 0, 0)
René Just Haüy Nicolas Steno
(1 1 0) (1 0 0) (0 1 0)
y French Danish
1801 1669
indices of parallel planes in-between are multiples of smallest. quartz

( 1/3 ∞ ∞ ) (3 0 0) Law of constant angles

Law of rationality of crystallographic indices
the planes in the middle contain no lattice points.
in X-ray crystallography, they are unique planes

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Miller Planes Interplanar Spacing

since the equation of a (Miller) plane is: the planes in a family are separated by a ┴ distance, d

x y z where a, b, and c are the intercepts

+ + = 1
a b c of the plane with x, y, z
(2 2 1)
1 1 1
can set: h = ,k = ,ℓ =
a b c

equation becomes: d

hx + ky + ℓz = 1
d = V[h2b2c2sin2 + k2a2c2sin2 + ℓ2a2b2sin2
Miller Planes given as ( h k ℓ ) + 2hℓab2c(coscos– cos) + 2hkabc2(coscos– cos)
+ 2kℓa2bc(coscos– cos)]–1/2

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