SOLID STATE CHEMISTRY

Basic concepts/terms.

Crystalline solids: highly regular arrangement of atoms, ions, molecules - periodic

(repeating)
Amorphous solids: no repeating pattern, only short range order, extensively disordered -
non crystalline (e.g. glasses)

We will focus on Crystalline solids :

- how do we describe them ? - lattices

- what types exist ? - metallic, ionic, extended covalent (or network), molecular.

- how can we study their structures ? - many ways, for example x-ray diffraction.

Crystallinity - have a repeating unit = unit cell

To define repeating unit use concept of a lattice

A lattice is "an infinite 1,2, or 3-D regular arrangement of points, each of which has
identical surroundings".

Any periodic pattern can be described by placing lattice points at equivalent positions
within each unit of the pattern.

To recover original pattern we add the motif to each lattice point.

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1-D lattices. The regular pattern of wagons below can be described by placing a lattice
point at the same place in each wagon. The arrangement of dots is the lattice, which has
a given repeat distance. The motif is the wagon. The pattern is recovered by stamping
the motif on each lattice point.
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2-D patterns: Planar lattices.

Consider each of the patterns below - what is the lattice and unit cell ?
Place lattice points at equivalent positions in the pattern, find smallest repeat unit that by
translation, can cover all space.
All of these patterns have the same Planar Lattice.(square), but each has a different motif.
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3-D Space Lattices.

Crystal structures repeat in 3 dimensions. The motif can be single atoms or groups of
atoms. Again we assign lattice points to the atomic structure and produce a Space
Lattice.

Space lattice + motif = Crystal Structure

There are 7 unique unit-cell shapes that can fill all 3-D space. These are the 7 Crystal
systems.

We define the size of the unit cell using lattice parameters (sometimes called lattice
constants, or cell parameters). These are 3 vectors, a, b, c. The angles between these
vectors are given by α (angle between b and c), β (angle between a and c), and γ
(angle between a and b).

The Seven Crystal Systems

Although there are only 7 crystal systems or shapes, there are 14 different crystal lattices,
called Bravais Lattices. (3 different cubic types, 2 different tetragonal types, 4 different
orthorhombic types, 2 different monoclinic types, 1 rhombohedral, 1 hexagonal, 1
triclinic). See below.

Real crystals always possess one of these lattice types, but different crystalline
compounds that have the same lattice can have different motifs and different lattice
parameters (these depend upon the chemical formula and the sizes of the atoms in the
unit cell). We will only concern ourselves with the cubic lattices, though we will refer to
the hexagonal lattice in passing.

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Bravais Lattices
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Cubic Lattices.
3 types; Simple cubic (also called primitive cubic), lattice points only at corners.

Body Centered Cubic (BCC), lattice points at corners and in middle of cube.

Face Centered Cubic (FCC) lattice points at the corners and in the middle of each face.

How many lattice points and/or atoms "belong" to a unit cell ?

Corners: The points at the corner of the cell are shared by the surrounding unit cells,
therefore each one is shared by 8 in total and is only "worth" 1/8 to each cell.

Faces : - these lattice points are shared by 2 cells, each one is "worth" 1/2 to each cell.

Body : - this is the sole possesion of that cell, worth 1.

Total number lattice points: primitive cubic = 8(1/8) = 1; FCC = 6x1/2 + 8(1/8) = 4; BCC
= 8(1/8) + 1 = 2.

Now that we know how to describe crystalline solids, let us examine different types
according to the nature of their bonding. We will begin with metallic solids, followed by
ionic solids, and extended covalent or framework solids.

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Cubic Lattices.
3 types; Simple cubic (also called primitive cubic), lattice points only at corners.

Body Centered Cubic (BCC), lattice points at corners and in middle of cube.

Face Centered Cubic (FCC) lattice points at the corners and in the middle of each face.

How many lattice points and/or atoms "belong" to a unit cell ?

Corners: The points at the corner of the cell are shared by the surrounding unit cells,
therefore each one is shared by 8 in total and is only "worth" 1/8 to each cell.

Faces : - these lattice points are shared by 2 cells, each one is "worth" 1/2 to each cell.

Body : - this is the sole possesion of that cell, worth 1.

Total number lattice points: primitive cubic = 8(1/8) = 1; FCC = 6x1/2 + 8(1/8) = 4; BCC
= 8(1/8) + 1 = 2.

Now that we know how to describe crystalline solids, let us examine different types
according to the nature of their bonding. We will begin with metallic solids, followed by
ionic solids, and extended covalent or framework solids.

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