CRYSTAL CHEMISTRY

Wh iis crystall chemistry?

What
h i
?
description and classification of crystals

Reading:
g
Basic West Ch 1
West Ch 8

bonding;
b di
composition-structure
iti
t t
relationships
l ti
hi
the conditions in which particular type of crystal structure is observed
structure-property
structure property relations

Common ways to describe crystals:

unit cell approach (specify size, shape and atomic positions)
close-packing approach (good for metals
metals, alloys
alloys, ionic structures
structures, covalent
networks, molecular and supermolecular solids)
space-filling
g po
polyhedron
y ed o app
approach
oac
space
67

CLOSE-PACKED CRYSTAL STRUCTURES

Consider the close-packing of incompressible (hard) spheres:
In 2D, regular close-packing requires an hexagonal array (HCP)

Most efficient way

to pack spheres of single size
6 nearest neighbors
Coordination number (CN): 6
In 3D, regular close-packing involves stacking 2D HCP arrays
CCP

Regular
(crystalline)
packing
ki

Irregular
packing

68

HEXAGONAL CLOSE-PACKED STRUCTURE

An HCP crystal is a close-packed structure with the stacking sequence ...ABABAB...
ABABAB

To construct:
1st layer: 2D HCP array (layer A)
2ndd layer:
l
HCP llayer with
i h eachh sphere
h placed
l d in
i alternate
l
interstices
i
i
in
i 1stt layer
l
(B)
3rd layer: HCP layer positioned directly above 1st layer (repeat of layer A)
ABABABAB

A
B
A

A
HCP is two interpenetrating simple hexagonal
lattices displaced by a1/3 + a2/3 + a3/2
69

HCP STRUCTURE
not a Bravais
avais lattice
Orientation alternates
with each layer

each sphere touches 12 equidistant nearest neighbors (CN = 12)

Six in plane, six out-of-plane

structure has maximum p

packingg ffraction possible
p
for
f single-sized
g
spheres
p
((0.74))
70

HCP STRUCTURE

ideal ratio c/a of

8 / 3 1.633

unit cell is a simple hexagonal lattice with a

two-point basis
a
(0 0 0)
(0,0,0)

{0002} planes are close packed

ranks in importance with FCC and BCC
Bravais lattices

(2/3,1/3,1/2)

Plan view

71

HCP STRUCTURE
about 30 elements crystallize in the HCP form

72

CUBIC CLOSE-PACKED STRUCTURE

A CCP crystal is a close-packed structure with the stacking sequence ...ABCABC...
ABCABC

To construct:
1st layer: 2D HCP array (layer A)
2ndd layer:
l
HCP llayer with
i h eachh sphere
h placed
l d in
i alternate
l
interstices
i
i
in
i 1stt layer
l
(B)
3rd layer: HCP layer placed in the other set of interstitial depressions (squares, C)
4th layer: repeats the 1st layer (A)
ABCABCABC
ABCABCABC
stacking
g
of HCP layers
along
body diagonals

C
It turns
t
outt that
th t th
the CCP structure
t t
is
i just
j t
the FCC Bravais lattice!
73

CCP STRUCTURE
CN = 12
12, packing fraction 0.74
0 74

{111} planes are close packed

4 atoms in unit cell
Plan view
74

CLOSE-PACKED STRUCTURES
most common are
a e HCP
C and CC
CCP

an infinite # of alternative stacking sequences exist

Example: silicon carbide has over 250 polytypes
e.g., 6H-SiC
stacking sequence ABCACB
75

STACKING FAULTS
Stacking faults are one or two layer interruptions in the stacking sequence that
destroy lattice periodicity

e.g., an <110> projection of an FCC lattice:

[111]
[110]
[110]

[001]

A
B
C

A
B
C

A
B
C
A
B
C

B
C
A
B
C

perfect FCC
ABCABCABC

missing
l
plane
of atoms

faulted FCC
ABCBCABC

The stacking fault is an example of a planar defect

stacking fault energy ~100 mJ m-22
results also in perpendicular linear defects called dislocations
76

EXAMPLE

InAs nanowires - <110> projection

77

Caroff, P. et al. Nature Nanotechnology 4, 50 - 55 (2009).

 CCP and HCP have veryy similar lattice energies

g
no clear cut trends
78

Nature

353, 147 - 149 (12 Sep 1991)

Rare Gases:
G
Ne, He, Ar,
A Kr, Xe (CC
(CCP))
79

gold nanocrystals
X. M. Lin

80

ANOTHER VIEW OF CLOSE PACKING

81

. It was
reviewed by a panel of 12 referees; the panel reported in 2003
2003, after 4 years of
work, that it was 99% certain of the correctness of the proof, but couldnt
verify all of the computer calculations. Hales and Ferguson (his student)
received the Fulkerson Prize for outstanding papers in the area of discrete
mathematics in 2009.
In 2003, Hales announced that he would pursue a formal proof of the
Conject re that could
Conjecture
co ld be verified
erified b
by comp
computer.
ter He estimates that the proof will
ill
be finished by 2023
http://en.wikipedia.org/wiki/Kepler_conjecture

PACKING FRACTIONS
The fraction of the total crystal volume that is occupied by spheres
CCP (and HCP)

radius

4 a 23

(
4
)
Vatoms

fraction
3 3 4 2 0.7405
Vcell
a
6

a 2

a 2
4

74%

BCC

SC

a 3
radius
4

4 a 33
2 (
)
fraction 3 3 4 0.6802
0 6802
a

68%

4 a3
( )
fraction 3 32 0.5236
a

52%
83

84

DENSITY CALCULATION
n: number
b off atoms/unit
/ i cell
ll

matoms nA 1

Vcell
N A VC

A: atomic mass
VC: volume of the unit cell
NA: Avogadros number
(6.0231023 atoms/mole)

Calculate the density of copper.

RCu = 0.128 nm, Crystal structure: FCC, ACu= 63.5 g/mole

n = 4 atoms/cell,,

VC a 3 ((2 2 R )3 16 2 R 3

(4)(63.5)
3

g
cm
8.89
/
[16 2(1.28 108 )3 (6.023 1023 )]
8.96 g/cm3 in the literature

85

INTERSTICIAL SITES IN CP STRUCTURES

A large number of ionic structures can be regarded as built of CP layers of anions
with the cations placed in interstitial sites

for everyy anion,, there is 1 Octahedral site and 2 Tetrahedral sites

86

Octahedral holes
coordinates:
di t
00
00
00

= O site
cavities have <100>
orientation
i t ti
87

Tetrahedral holes in CCP

T+ sites:

T- sites:

cavities have <111> orientation

88

Holes in HCP
O sites:
2/3,1/3,1/4
2/3,1/3,3/4
, ,
T+ sites:
1/3 2/3 1/8
1/3,2/3,1/8
0,0,5/8

(1/3,2/3,1/2)

(0,0,0)
a2

a1

T- sites:
0,0,3/8
, ,
1/3,2/3,7/8
89

LOCATION OF OCTAHEDRAL HOLES

90

LOCATION OF TETRAHEDRAL HOLES

(3/8 of a unit cell directly

above/below each anion)

91

SIZE OF OCTAHEDRAL CAVITY

Onlyy cations smaller than the diameter of the cavity
y can fit
without forcing the anion lattice to expand

from cell edge

a 2rM 2rX
from face diagonal

M = cation
ti
X = anion

a 2 2rX

.
The cation radius must be
< 41% of the anion radius

SIZE OF TETRAHEDRAL CAVITY

The tetrahedral holes are twice as
numerous but six times smaller in volume

The cation radius must be

< 23% of the anion radius

EUTACTIC STRUCTURES
Structures in which the arrangement of ions is the same as in a close packed array
but the ions are not necessarily touching

Within certain loose limits (given by the radius ratio rules), cations
too large to fit in the interstices can be accommodated by an
expansion of the anion array
anions dont like to touch anyway
modern techniques show that, in many cases, anions (cations) are
not as large
g ((small)) as ppreviouslyy thought
g
we still describe eutactic structures as CCP or HCP lattices
with ions in some fraction of the interstitial sites
94

CRYSTALS THAT CAN BE DESCRIBED IN

TERMS OF INTERSTITIAL FILLING OF A
CLOSE-PACKED STRUCTURE

95

SOME EUTACTIC CRYSTAL STRUCTURES

Variables:
1)
2)

anion layer stacking sequence: CCP or HCP array?

occupancy of interstitial sites

96

97

NaCl (ROCK SALT, HALITE) STRUCTURE

(CCP 100% O
(CCP,
Oct.
t H
Holes
l Fill
Filled)
d)

Space Group = Fm3m

Lattice = FCC
Basis = Cl (0,0,0), Na (,,)
Coordination = 6, 6
Cation Coord. Octahedron
Anion Coord.
Coord Octahedron
Connectivity Edge sharing octahedra
with faces parallel to {111}
4 NaCl in unit cell

98

POLYHEDRAL REPRESENTATION
shows the topology and indicates interstitial sites
tetrahedra and octahedra are the most common shapes
Rock Salt:
Array of edge sharing NaCl6 octahedra
Each
h octahedron
h d
shares
h
allll 12 edges
d
Tetrahedral interstices

Galena (PbS)

99

ROCK SALT - OCCURANCE

Very common (inc. 'ionics', 'covalents' & 'intermetallics' )
Most alkali
lk l halides
h l
(CsCl,
(
l CsBr, CsI excepted))
Most oxides / chalcogenides of alkaline earths
Many
M n nitrides,
nit id s carbides,
bid s h
hydrides
d id s ((e.g. Z
ZrN,
N TiC
TiC, N
NaH)
H)

100

COMPLEX ION VARIANT OF ROCK SALT

space group = Pa3

S 22 dimers oriented along <111>

101

ZINC BLENDE (ZnS, SPHALERITE)

(CCP T+
(CCP,
T Holes
H l Filled)
Fill d)

Space Group = F43m

Lattice = FCC
B i = S (0,0,0),
Basis
(0 0 0) Zn
Z (,,)
( )
Coordination = 4, 4
Cation Coord. Tetrahedron
Anion Coord. Tetrahedron
Connectivity Corner sharing Tetra.
4 ZnS in unit cell

102

ZINC BLENDE

GaAs

bonding is less ionic than in rock salt

common for Be, Zn, Cd, Hg chalcogenides (i.e., ZnS, ZnSe, ZnTe)
common for III-V compounds (B, Al, Ga, In with N, P, As, Sb)

103

DIAMOND STRUCTURE
S
Same
as sphalerite,
h l it b
butt with
ith id
identical
ti l atoms
t
iin all
ll positions
iti

Space Group = F43m

Lattice = FCC
B i = C (0
Basis
(0,0,0),
0 0) C (,,)
( )
Coordination = 4
g Tetra.
Connectivityy Corner sharing
8 C atoms per unit cell
104

FLUORITE (CaF2) & ANTIFLUORITE (Na2O)

Fluorite : CCP of Ca2+, 100% Tetra. Holes Filled with FAnti-fluorite : cation and anion positions are reversed

Ca2+

Space Group = Fm3m

Lattice = FCC
Basis = Ca2+ (0,0,0),
(0 0 0) F- (,,)
( ) & (
(,,)
)
Coordination = 8, 4 (fluorite)
Cation Coord. Cubic
Anion Coord. Tetrahedral
Connectivity Edge sharing FCa4 tetrahedra or edge sharing CaF8 cubes
4 CaF2 in unit cell

105

ALTERNATIVE REPRESENTATIONS

Ca2+

Displacing the unit cell by of a body diagonal emphasizes the cubic cation coordination:

F-

106

FLUORITE / ANTIFLUORITE
Ca2+

origin of the term fluorescence

(George Stokes, 1852)
fluorite common for fluorides of large,
divalent cations and oxides of large
tetravalent cations (M2+F2 and M4+O2)
antifluorite common for
oxides/chalcogenides of alkali earths
ea ths ((M2O)
Eu

2+

CaF2

107

FLUORESCENT MINERALS

= fluorite

108
http://en.wikipedia.org/wiki/Fluorescence

COMPARING NaCl, ZnS, Na2O

NaCl

ZnS

Na2O

109

110

Li3Bi EXAMPLE

111

NiAs STRUCTURE
(HCP, 100% Oct. Holes Filled)

Space Group = P63/mmc

Lattice = Primitive hexagonal
Basis = As (0,0,0) & (2/3,1/3,1/2)
Ni (1/3,2/3,1/4) & (1/3,2/3,3/4)
Coordination = 6, 6
Cation Coord. Octahedron
Anion Coord.
Coord Trigonal prism
Connectivity Edge/face sharing Oct.
or edge-sharing trigonal prisms
2 NiAs in unit cell

112

Alternative unit cell with Ni at the origin:

113

NiAs

Transition
Transition metals with
chalcogens, As, Sb, Bi
e.g. Ti(S,Se,Te);
( , , , )
Cr(S,Se,Te,Sb);
Ni(S,Se,Te,As,Sb,Sn)
114

WURTZITE (ZnS) STRUCTURE

(HCP T+
(HCP,
T Holes
H l Filled)
Fill d)

Space Group = P63mc

Lattice = Primitive hexagonal
B i = S (0,0,0)
Basis
(0 0 0) & (2/3
(2/3,1/3,1/2)
1/3 1/2)
Zn (0,0,5/8) & (2/3,1/3,1/8)
Coordination = 4, 4
Cation Coord. Tetrahedron
Anion Coord. Tetrahedron
Connectivity Corner sharing Tetra.
2 ZnS in unit cell

115

ZnO

Projections perpendicular to close-packed planes

116

117

Very different next-nearest neighbor coordinations & beyond

118

HCP VERSION OF CaF2?

N structures
No
t
t
are known
k
with
ith all
ll T
Tetra.
t
sites
it (T
(T+ and
d T-)
T ) fill
filled
d iin HCP
- i.e. there is no HCP analogue of the Fluorite /Anti-Fluorite structure
Why?
The T+ and T- interstitial
sites above and below a layer
of close-packed spheres in
HCP are too close to each
other (distance = 0.25c) to
tolerate the coulombic
repulsion generated by filling
with like-charged ions.

119

Face-linking is unfavorable

RUTILE STRUCTURE (TiO2)

((distorted HCP,, 50% Oct. Holes Filled))

Ti

(0,0,0)
Space Group = P42/mnm
Lattice = Primitive tetragonal
Basis = Ti (0,0,0) & (,,)
O (0
(0.3,0.3,0),
3 0 3 0) (0
(0.7,0.7,0),
7 0 7 0) (0
(0.8,0.2,0.5),
8 0 2 0 5) (0.2,0.8,0.5)
(0 2 0 8 0 5)
Coordination = 6, 3
Cation Coord. Octahedral
Anion Coord. Trigonal planar
Connectivity chains of edge-sharing Oct.
along c axis, linked by vertices
2 TiO2 per unit cell

120

ANATASE STRUCTURE (TiO2)

(di t t d CCP,
(distorted
CCP 50% Oct.
O t Holes
H l Filled)
Fill d)

Ti

a = 3.776
b=3
3.776
776
c = 9.486
Volume anatase TiO2 cell: 136.25 3
rutile TiO2 cell: 62.07 3

Space Group = I41/amd

Lattice = body-centered tetragonal
Coordination = 6, 3
Cation Coord. Octahedral
Anion Coord. Trigonal planar
Connectivity chains of edge
edge-sharing
sharing Oct.
Oct
along c axis, linked by vertices and edges
4 TiO2 per unit cell

121

RUTILE AND ANATASE

chains of edge sharing oct.,

linked at corners

greater density of edge sharing

a bit less stable
122

CdI2 STRUCTURE
(HCP with
(HCP,
ith Cd in
i Oct.
O t Holes
H l off alternate
lt
t llayers))
A layered crystal

Cd

Space Group = P3m1

Lattice = Primitive trigonal
B i = Cd (0,0,0)
Basis
(0 0 0)
I (2/3,1/3,1/4) & (1/3,2/3,3/4)
Coordination = 6, 3
Cation Coord. Octahedron
Anion Coord. Trigonal pyramid
Connectivity sheets of edge-sharing Oct.
1 CdI2 per unit cell

123

Alternative
unit cell
with Cd at
the origin:

CdI6 units

NiAs6 units
124

CdI2 - OCCURANCE
Iodides of moderately polarizing cations; bromides and
chlorides of
f strongly
g y polarizing
p
g cations;;
e.g. PbI2, FeBr2, VCl2
Hydroxides of many divalent cations
e.g. (Mg,Ni)(OH)2
Di-chalcogenides of many quadrivalent cations
e.g. TiS2, ZrSe
Z S 2, CoTe
C T 2

125

CdCl2 STRUCTURE
The CCP analogue of CdI2
(CCP, with Cd in Oct. Holes of alternate layers along [111])

CdCl6 octahedra
Space Group = R32/m

Chlorides of moderately polarizing cations

e.g. MgCl2, MnCl2
Di-sulfides of quadrivalent cations
e.g. TaS2, NbS2 (CdI2 form as well)

126

Formula

Type and fraction

of sites occupied

CCP

HCP

AB

All octahedral

NaCl
Rock Salt

NiAs
Nickel Arsenide

Half
tetrahedral
(T+ or T-)

ZnS
Zinc Blende

ZnS
Wurtzite

A2B

All tetrahedral

Na2O Anti-Fluorite
N
A ti Fl it
CaF2 Fluorite

not known

A3B

All octahedral
& ttetrahedral
t h d l

Li3Bi

not known

AB2

Half octahedral
(Alternate layers
full/empty)

CdCl2 (Cadmium Chloride)

CdI2 (Cadmium Iodide)

Half octahedral
(Ordered
framework
arrangement)

TiO2 (Anatase)

CaCl2
TiO2 (Rutile)

Third octahedral
Alternate layers
2/ full/empty
3

YCl3

BiI3

AB3

127

PEROVSKITE STRUCTURE ABO3 (CaTiO3)

(CCP of Ca & O , 25% Oct. Holes Filled by Ti)

A-Cell

B C ll
B-Cell
Space Group = Pm3m
Lattice = Primitive cubic
B i = Ti (0
Basis
(0,0,0),
0 0) Ca
C (,,),
( )
O (,0,0), (0,1/2 ,0) & (0,0,)
Coordination = Ca-12 ; Ti-6; O-6
Ca Coord. Cuboctahedron
Ti Coord. Octahedron
O Coord. distorted octahedron (4 Ca, 2 Ti)
1 CaTiO3 per unit cell

An extremely important class of ABX3

compounds:
Magnetoresistance
Ferroelectricity
Multiferroics
Superconductivity
d
Catalysis (fuel cells)
Spin transport
128

PEROVSKITE CONNECTIVITY

B-Cell

3D network of corner-sharing
octahedra

Network of face-sharing
cuboctahedra
129

Perovskites: the most widely studied oxide structure

Wide range of chemistries possible
- thousands of examples known
Cubic, tetragonal, and orthorhombic symmetries are common

Unique properties of perovskites

- high Tc cuprate superconductors
- Colossal Magneto-Resistance
Magneto Resistance (La,SrMnO
(La SrMnO3)
- fast ion conduction (Li+, O2-), batteries, fuel cells
- mixed electronic/ionic conduction, fuel cells
- oxidation/reduction catalysts
- ferroelectric / piezoelectric ceramics (BaTiO3, Pb(ZrTi)O3)
- important mineral structure in lower mantle (MgSiO3, pyroxene)
q
y filters for wireless communications : Ba(Zn
( 1/3Ta2/3))O3
- frequency
130

Perovskite Structure: ABX3

Tolerance factor (t):

rA rX
t
2(rB rX )

B
A-Cell
t
>1
0.9 - 1.0

Effect
A cation too large to fit in
interstices
ideal

0.71 - 0.9 A cation too small

< 0.71

A cation same size as B cation

Likely structure
Hexagonal
perovskite
Cubic perovskite
Orthorhombic
perovskite
Possible close packed
131
lattice

PEROVSKITES
Most perovskites contain distorted octahedra and are not cubic
cubic, at least at lower
temperatures. These distortions give perovskites a rich physics.

symmetry at 25
25C
C
BaTiO3: Ba2+
Ti4+
O2-

r = 1.56
r = 0.68
r = 1.26

t = 1.03 - tetragonal

KNbO3:

K+
1.65
Nb5+ 0.78

t = 1.01 - orthorhombic

LiNbO3:

Li+
1.06
Nb5+ 0.78

t = 0.81 trigonal

LiNbO3 : ferroelectricity, Pockels effect, piezoelectricity, photoelasticity,

nonlinear optical polarizability
132

133

Reading: West Ferroelectricity

C m-2

V m-11

134

DI- , PARA- , AND FERROELECTRICS

response
p
of atom to applied
pp
E field

dipole moment: p = qd = E
polarization: P = p/V

P = 0eE
p

dielectric polarization

P : polarization (C/m2)
0: vacuum permittivity 8.85 x 10-12 C2 N-1 m-2
e: electric
l
susceptibility
bl
(unitless)
(
l
)
E : electric field (V/m, or N/C)

paraelectric polarization

linear: P = 0eE

nonlinear

no P without E

no P without E

ferroelectric polarization
residual (zero-field)
(zero field) polarization
reversible direction of residual P
very large susceptibilities
135

WHY IS BaTiO3 FERROELECTRIC

ferroelectric phase transition

> 120C cubic, not FE
< 120C tetragonal, FE
transition occurs at the

Curie temperature, Tc

~0.1 displacement

dielectric constant

r = e + 1

137

FERROELECTRIC HYSTERESIS LOOPS

remnant polarization, PR

saturation polarization, Ps

dipoles aligned up

coercive field
field, EC

dipoles aligned down

138

ORDERED ELECTRIC DIPOLE PHASES

ferroelectric (BaTiO3)
parallel ordering below Tc

antiferroelectric (PbZrO3)
antiparallel ordering below Tc

E field can induce

ferroelectric state

ferrielectric (Bi4Ti3O12)
net spontaneous polarization in only certain direction(s)

139

CURIE TEMPERATURE
Thermal energy destroys the ordered electric dipole state
state. The temperature above
which this order-disorder phase transition occurs is the Curie temperature, Tc.

Above Tc, the material is often paraelectric.

ordered
F / AF

randomized
orientation

Note:
These curves
omit the
spikes in P
at Tc

140

PHASE DIAGRAMS

141

K2NiF4 STRUCTURE (La2CuO4)

Many complex
complex structures are composed of simple,
simple familiar building blocks
blocks.
The high-Tc copper oxide superconductors are an example.

Doped La2CuO4 was the first (1986) High-Tc Superconducting Oxide (Tc ~ 40 K)
B d
Bednorz
& Mller
Mll were awarded
d d a Nobel
N b l Prize
Pi
La2CuO4 may be viewed as if constructed from an ABAB... arrangement of
Perovskite cells - known as an AB Perovskite!
B

2 La2CuO4 per unit cell

142

ALTERNATE VIEWS OF La2CuO4

We may
y view the structure as based on:
1. Sheets of elongated CuO6 octahedra, sharing only vertices
2. Layered networks of CuO46-, connected by La3+ ions

143

COMMON STRUCTURAL FORM

Cations form
FCC with O22interstitials

Common structural motif of vertex-linked CuO4 squares

This motif occurs in all the high-TC superconducting copper oxides
The structures differ in the structure of the 'filling' in the 'sandwich
of copper oxide layers - known as Intergrowth Structures
144

YBa2Cu3O7: THE 1,2,3 SUPERCONDUCTOR

the first material to superconduct at LN2 temperature, Tc > 77 K
YBa2Cu3O7 can be viewed as an Oxygen-Deficient Perovskite

145

POLYHEDRAL REPRESENTATION OF YBCO

Two types
T
t p s of
f Cu
C sites:
sit s:
1) Layers of CuO5 square pyramids
2) Chains of vertex-linked CuO4 squares

CuO2
BaO
CuO
BaO
CuO2
Y
CuO2

146

SPINEL STRUCTURE AB2O4 (MgAl2O4)

(CCP, Mg in 1/8th of Tetra. Holes and Al in 50% of Oct. Holes)

a = 8.08

Space Group = Fd3m

Lattice = FCC
Coordination = Mg-4; Al-6; O-4
Mg Coord. Tetrahedron
Al Coord. Octahedron
Connectivity chains of Edge-sharing AlO6
octahedra, linked by MgO 4 tetra.
8 MgAl2O4 per unit cell (56 atoms)

extremely flexible structure, adopted

by 100s of compounds
normal spinel: 8 A in Tetra., 16 B in Oct.
inverse spinel: 8 B in Tetra ,
8 A and 8 B in Oct.
intermediate cations distributions also
147
occur.

148

SPINELS - OCCURANCE
Aluminium spinels:
Spinel MgAl2O4, after which this
class of minerals is named
Gahnite - ZnAl2O4
H
Hercynite
i - FeAl
F Al2O4
Iron spinels:
Magnetite - Fe3O4
Franklinite - (Fe,Mn,Zn)(Fe,Mn)2O4
Ulvspinel - TiFe2O4
Jacobsite - MnFe2O4
Trevorite - NiFe2O4
Ch
Chromium
i
spinels:
s i ls:
Chromite - FeCr2O4
Magnesiochromite - MgCr2O4
Others with the spinel
p
structure:
Ulvspinel - Fe2TiO4
Ringwoodite - Mg2SiO4, an abundant
olivine polymorph within the Earth's
mantle from about 520 to 660 km
depth, and a rare mineral in
meteorites

149

CRYSTAL FIELD STABILIZATION ENERGY

In transition metal compounds,
compounds d electron effects such as crystal field
stabilization energy (CFSE) can be important in determining structure.

crystal field splitting diagrams

e.g. MF2 compounds (high spin rutile)
oct =

tetra =

CFSEoct = (0.4 #t2g 0.6 #eg) oct

tetra = (4/9)oct

No CFSE
150

CATION SITE PREFERENCES IN SPINELS

The larger CFSE of metal ions in octahedral sites is sometimes an important
f
factor
in d
determining spinell structures ((normall vs inverse).
)

Normal - [A]tet[B2]octO4

Inverse - [B]tet[A,B]octO4

= fraction of A in oct. sites

= 0 is normal, = 1 is inverse

In the absence of CFSE effects: 2,3 spinels tend to be normal (MgAl2O4)

4,2 spinels tend to be inverse (TiMg2O4)

In 2,3 spinels,
l CFSE
E favors
f
the
h following:
f ll
1) Chromium spinels (Cr3+) are normal
2) Magnetite (Fe3O4) is inverse b/c
Fe3+ has zero CFSE, while Fe2+ prefers oct.
3) Mn3O4 is normal b/c Mn2+ has no CFSE

151

CORUNDUM STRUCTURE (-Al2O3)

(HCP 2/3 off Oct.
(HCP,
O t Holes
H l filled)
fill d)
Space Group = R3c
Lattice = Primitive trigonal
Coordination = 6, 4
Cation Coord.
Coord Octahedron
Anion Coord. distorted tetrahedron
Connectivity edge, face-sharing Oct.
6 Al2O3 per unit cell

Ruby (Cr), sapphire (Fe, Ti, Cr), Fe2O3

152