1.

Metallic Bonding

The simplest description of bonding in metals is the “electron-sea” or “electron-

gas” model. In this model, valence electrons are delocalized and free to move
throughout the metallic crystal. In this model, the mobility of these valence
electrons accounts for the electrical and thermal conductivity of metals.
However, as molecular orbital theory provided an improved model of bonding in
molecules relative to the valence bond or Lewis approach, it also provides an
improved model for metals. Molecular orbital theory applied to crystals is often
called band theory.
The 2s orbitals from two Li atoms interact to produce a bonding M.O. and anti-
bonding M.O. We will modify this diagram slightly by placing all of the A.O.s on
one side and the M.O.s on the other. Now consider the interaction of 4 Li atoms.
Observe that there are as many M.O.s as there are interacting A.O.s Furthermore,
only the bonding MOs are occupied, irrespective of the number of intercting atoms.
Also, the minimum and maximum energies roughly correspond to those in the
diatomic molecule.
Crystals may be regarded as huge molecules, where the number of atoms is very
large–on the order of Avogadro’s number. We often differentiate between metals,
insulators and semiconductors.
Orbitals in crystals are referred to as crystal orbitals. These range over the entire
crystal, but they may have greater probability at one type of atom (as in ionic
crystals).
Crystal orbitals have energies similar to the A.O. energies of the atoms forming the
crystal.
Observations:
1. As many orbitals correlate with each A.O. as there are atoms in the crystal.
2. When N is very large (approaching macroscopic dimensions), crystal orbital
energies are very close together and they form a BAND.
3. Energies of the crystal orbitals lie within limits. These limits are the BAND
WIDTH and the band width is similar to the gap between two MOs in a diatomic
molecule.
The size of the band width depends on the strength of interaction of AOs of
neighboring atoms in the crystal.

Consider Bands from two atomic orbitals:

The band gap is smaller than the energy gap between AOs in the isolated atom.
Band Gap depends on:
1. Energy gap between AOs in the atom
2. Widths of the bands

ENERGY BANDS in LITHIUM (lowest energy configuration = ground state)

Note: Band widths, gaps, overlaps

Electronic configuration of atom and crystal
1s AO and 1s band are each completely filled.
2s AO and 2s band are each half filled.

Energy Bands in Be

Insulators and semiconductors

Structures of Metallic Crystals

The maximum attraction between atoms in obtained when each atom is
surrounded by the largest possible number of other atoms. In order to visualize the
structure of crystals, we need only consider how identical spheres pack into a
given space.
One possible arrangement involves all the spheres packed into rows side by side.
Successive layers are then placed upon the previous layers with atoms directly
above atoms in the previous layer. This arrangement is referred to as “Simple
Cubic” and is not very efficient.

Simple Cubic (SC, also called primitive cubic)

1 atom at the corner of each unit cell.

1 net atom per unit cell.
Coordination number (number of nearest neighbors) = 6.
52% packing efficiency.
Only Po is known to crystallize in a SC lattice.

Suppose that instead of placing the atoms in the second layer

directly above those in the first, we offset them slightly. This
provides for somewhat more efficient packing.

Body Centered Cubic (BCC)

1 atom at each corner plus one in the center of the unit cell
2 net atoms per unit cell
Coordination number = 8
68% packing efficiency
e.g. Na, V, K, Fe (low temp)
When a single layer of spheres is packed in its most efficient manner, we find that
each sphere is surrounded by six other spheres as shown in the diagram below.
The next layer of atoms (blue) rests in the “dimples” of the first layer as shown.
When the third layer (red) is placed, the atoms can go into either of two sets of
“dimples.” If the atoms of the third layer go into the dimples directly above atoms of
the first layer, an ABABAB pattern is established. This ABABAB pattern is referred
to as a hexagonal closepacked (hcp) lattice.
On the other hand, if the atoms of the third layer occupy dimples that are above
dimples in the first layer, an ABCABC pattern is established. This is referred to as
a cubic close- packed (ccp) lattice. The ccp lattice is identical to the face centered
cubic lattice. In each of the close packed lattices (hcp and ccp), the coordination
number or number of nearest neighbors is 12. You can calculate the packing
efficiency of the close packed arrangements. In either case, the atoms occupy
74% of the total volume of the crystal. Many metallic solids crystallize in a close
packed arrangement (either hcp or ccp). However, an appreciable number
crystallize in a body centered cubic (BCC) array. The packing efficiency of the
BCC arrangement can be calculated and is 68%.

Face-centered cubic (FCC, also called Cubic Close Packed, CCP)

1 atom at each corner plus one atom on the center of each face.
4 net atoms per unit cell
 Coordination number = 12
74% packing efficiency
e.g. Cu, Al, Ag, Au, Fe (higher temp)

Counting Atoms

Each atom at the corner of a unit cell is shared by eight different unit cells.
Therefore, each corner atom contributes 1/8 to any one unit cell.
Each atom on the center of a face of the unit cell is shared by two different unit
cells. Therefore each atom on the center of a face contributes ½ to any one unit
cell.
Each atom on the center of an edge of the unit cell is shared by four different unit
cells. Therefore, each edge centered atom contributes ¼ to any one unit cell.
An atom in the center of a unit cell belongs exclusively to that unit cell.
Simple Cubic–atoms touch along an edge as shown to the right. The length of the
unit cell edge (e) is equal to 2 times the radius of
the atom.
e = 2r
Body Centered Cubic-atoms touch along the cube diagonals
b = cube diagonal = 4r

Face Centered Cubic–atoms touch along a face diagonal

f = face diagonal = 4r
Calculations Involving Unit Cell Dimensions

Once we know something about the unit cell type and dimensions, a whole series
of interesting calculations become possible. For example, it is possible to calculate
the density of metals or ionic substances by knowing the atomic or ionic radii and
the specifics of the unit cell.
Example:
Estimate the density of Po if the atomic radius is assumed to be 190 pm.
Example:
Na crystallizes in a body centered cubic lattice. The atomic radius of Na is 186 pm.
What is the density of Na?