Perovskite Structure and Derivatives

SrTiO3 - Cubic Perovskites

General formula: ABO3 where A and B are cations.
The easiest way to visualize the structure is in terms
of the BO6 octahedra which share corners infinitely in
all 3 dimensions.
The A cations occupy every hole which is created by
8 BO6 octahedra, giving the A cation a 12-fold
oxygen coordination, and the B-cation a 6-fold
oxygen coordination. In the example shown here,
(SrTiO3) the Sr atoms sit in the 12 coordinate A site,
while the Ti atoms occupy the 6 coordinate B site.

There are many ABO3 compounds for which the ideal cubic structure is distorted to a
lower symmetry (e.g. tetragonal, orthorhombic, etc.)

Spinels
Stoichiometry = AM2X4
Space Group = Fd3m (227)
They take their name from MgAl2O4

The spinel structure is a rather complex

arrangement based upon a cubic close packed
anion array, with 1/2 of the octahedral sites
filled and 1/8 of the tetrahedral sites filled. In
each cell, there are 64 tetrahedral sites and 32
octahedral sites (the same as the number of
oxygen per unit cell, that is, 32).

spinel
A M X

A polyhedral based view of the structure

reveals chains of edge-sharing octahedra,
together with tetrahedra that are isolated from
each other
It is one of the most prevalent structure types
for ternary oxides and sulfides.

Spinels
Spinels can be classified as either normal or
inverse, depending upon the cation distribution
Normal spinels are contain A cations on the
tetrahedral sites and M cations on the octahedral
sites, as depicted in the description below

In contrast, the tetrahedral sites in an inverse spinel are

occupied by the M cations and the octahedral sites by a
50:50 mixture of A and M cations.
One of the most intensively studied spinel compounds is magnetite, Fe3O4. Magnetite is an
inverse spinel, due to the fact that the tetrahedral sites are occupied by Fe3+, while the
octahedral sites are occupied by 50:50 mixture of Fe2+ and Fe3+.
The structure of magnetite can be approximated as a cubic unit cell with
composition (Fe3+)8[Fe2+1/2 Fe3+1/2]16 O32
Total n. of Fe atoms per cell = 8+16=24, Fe:O ratio = 24/32 = 3/4
Therefore we write Fe3O4

Crystallogrpahic computing
Some definitions:

scalar product between two vectors

and

cross product between two vectors

and

product (rows by columns) between two matrixes

transposed matrix of
0, , ,

(i.e. exchange

with

and

a coordinate system in which the origin and three basis vectors

are fixed

Vector in a coordinate system 0, , ,

X: coordinate matrix

A: matrix of the basis vectors

In a coordinate system 0, , ,
vectors are:

the scalar products between the basis

cos
cos
cos

90 :

In a cartesian coordinate system (where

0
0
0

In the case of crystal systems, were a, b, c represent the basis vectors of the
unit cell, the above equalities (
0, etc.) apply only to tetragonal,
orthorombic and cubic systems!
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Let us now consider the scalar product

This can be written as:

cos

cos

cos

In matrix notation:

G is the metric tensor. Its element define the moduli of a, b and c and the
angles between them

Some insights into the metric tensor G

In cartesian coordinates the metric tensor becomes:

0
0

0
0

And indeed, in cartesian coordinates:

The metric tensor G can be considered as a machine with two slots: one for
a row vector, one for a colum vector. Enter these vectors in the slots, and you
will get their scalar product!
row vector
= a scalar (i.e a number)!
Metric tensor
column vector

Scalar product

If

, then

cos

cos

cos

Which gives the square modulus of a vector

In a diagramatic form: 1) take a column vector; 2) make a row vector
from it; 3) enter both in the slots of G; 4) get the square modulus!
= square modulus (i.e a number)!
column vector

Make it a row vector

Fill the slots of the

Metric tensor

Remember: without a metric tensor, you cannot calculate things like

scalar products or moluli!!!!
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More insights into the metric tensor G

cos

cos
cos

cos
cos

cos

The value of the determinant is:

det

cos

cos

One can demonstrate that is equal to

defined by a, b and c

cos

2cos cos cos

, that is, the square volume of the cell

Scalar triple product:

Lets figure out a geometric meaning of this. Lets look at the cell
with the b and c axis in the plane
sin

sin

c
So,
is a vector with modulus
equal to the area of the A face of the
cell. Its direction is perpendicular to the A face:
If we divide

by its modulus, we get:

This is a unit vector with the same direction as

Now let us consider:

This gives then the projection of the basis vector a on

the direction defined by the unit vector .
It is therefore the heigth of the parallelepidep with the
face A as a base.
The volume V of the parallelepided (i.e. the unit cell) is then given by:

For a scalar triple product the following rule holds:

Which basically tells us that we can choose any of the faces (A, B, C) as the base for
the parallelepid, and then consider the normal to it as the direction of the heigth. We
will always get the same value for the volume of the cell.

The reciprocal lattice

Let a, b, c be the elementary translations of a space lattice, which we call
the direct lattice
We define now a second lattice, called the reciprocal lattice, which is
defined by translations a*, b* and c* satisfying the following relations:

The first equation tells us that is normal to the plane

, , is normal to the plane , . For example for

The second equation fixes the modules of

and

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Since

is normal to the plane

, it must be proportional to the cross product

But then, since the following relation holds

This can be rewritten as

1
Therefore:

In terms of moduli:
1

sin

sin

sin

...And obviously the reciprocal of the reciprocal lattice is the direct lattice:
1

: volume of the unit cell in the reciprocal lattice

...But, what is it exacly a reciprocal lattice? Let us look at the simple case of an
orthorombic lattice (Ratios a:b:c unrestricted, Angles = = =90)
1

sin

b*=1/b

c*=1/c

b
a

a*=1/a

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In other cases however, where the angles differ from 90, we would have
something like this, for example:

sin

sin

sin

Black dots: direct lattice

Yellow dots: its reciprocal lattice

15

It also exemplifies a lot the crystallographic calculations. Example:

and

are two vectors of the direct and reciprocal space, respectively

Let us consider their scalar product, which takes a very simple form:

X X

This property will be very useful in the theory of diffraction

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Consider the vector

of the reciprocal space

C

Consider also the family of planes (hkl) in the direct space

We recall the plane of the family (hkl) closest to the origin:

C

Consider the vectors B-A, C-A and C-B

B

B
A

is then perpendicular to the plane, therefore to the

(hkl) family

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is perpendicular to the (hkl) family

.This is the interplanar distance, or

Consider
equivalently state the distance from the origin
of the plane nearest to it.

can be calculated by the scalar product of

with the unit vector defined along the
direction of , which is . Therefore:

(hkl) family of planes

We have the noteworthy result that

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How can we make use of this important relation?

We can use them to build a reciprocal lattice starting from the direct lattice. Example:
Consider the direct lattice

b
0

19

How can we make use of this important relation?

We can use them to build a reciprocal lattice starting from the direct lattice. Example:

Take the 010 plane closest to the origin

010

b
0

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How can we make use of this important relation?

We can use them to build a reciprocal lattice starting from the direct lattice. Example:
Draw the

vector of the reciprocal lattice normal to it

010

010

b
0

This identifies the 010 lattice point of the reciprocal lattice

21

How can we make use of this important relation?

We can use them to build a reciprocal lattice starting from the direct lattice. Example:
Do the same for the (110) plane

010

110

b
0

a
110

This identifies the 110 lattice point of the reciprocal lattice

22

How can we make use of this important relation?

We can use them to build a reciprocal lattice starting from the direct lattice. Example:
Do the same for the (210) plane

010

110

210

b
0

210
This identifies the 210 lattice point of the reciprocal lattice
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How can we make use of this important relation?

We can use them to build a reciprocal lattice starting from the direct lattice. Example:
Do the same for the (310) plane

010

110

310

210

b
0

310
This identifies the 310 lattice point of the reciprocal lattice
And now we start seeing a row in the reciprocal lattice....

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How can we make use of this important relation?

We can use them to build a reciprocal lattice starting from the direct lattice. Example:
Do the same for other planes....

010

b
010
0

110

100

310

210

300

200

25

How can we make use of this important relation?

We can use them to build a reciprocal lattice starting from the direct lattice. Example:
Do the same for other planes....

010

b
010
0
0 0

110

100

1 0

210

200
2 0a

310

300

3 0

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How can we make use of this important relation?

So that the whole reciprocal lattice is built

b*
b
0

*
a*

For a 2D lattice:
b* a
a* b
V=absin
1
1

sin
1
1

sin

27

An interactive example of a 2D
reciprocal lattice

28

Reciprocal lattice
demo

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Reciprocal lattice
Consider the following 2D lattice

...and its reciprocal lattice

b*
b
0

a*

Reciprocal lattice
Forget for a moment about the reciprocal lattice

b
0

Reciprocal lattice
Now add one lattice poit at the center of
each cell in the 2D lattice

b
0

Reciprocal lattice
To stay with a primitive cell, we need to
take a different choice for the lattice
vectors, for instance:

b
0

Reciprocal lattice
However, this forces us to make a new choice also for the
primitive cell of the reciprocal lattice

b*
b

0
a*

For a 2D lattice:
b* a
a* b
V=absin
1
1

sin
1
1

sin

Reciprocal lattice
The reciprocal lattice is then....

b
0

b*

*
a*

A comparison

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FCC lattice
Relationship between the fcc and the primitive
rhombohedral unit cell
The primitive translational vectors of the FCC
lattice are:
1
2
1
2
1
2

:orhogonal unit vectors (cartesian unit vectors)

Volume of the primitive cell:

1
4
37

BCC lattice
Relationship between the bcc and the primitive
rhombohedral unit cell

1
2
1
2
1
2

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Reciprocal lattice of the FCC lattice

1
2
1
2
1
2

Let us calculate the primitive translational vector of the reciprocal lattice:

=
1

1
1

similarly:
1

1
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The primitive translational vectors of the lattice reciprocal to the FCC lattice are
therefore:
1

As can be seen below, these (apart from a scale factor) are primitive translational
vectors of a BCC lattice:

Therefore, the reciprocal of a FCC

lattice is a BCC lattice!
Conversely, the reciprocal of a
BCC lattice is a FCC lattice!
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