Solid State Physics

Homework Set 2
Solutions
Greg Balchin

Ibach and L
uth Problem 2.3

In order to answer this question we must distinguish between an ordered system and a disordered
system. An alloy, consisting of atoms A and B, is disordered if the A and B atoms are arranged
randomly on lattice sites. A disorderd alloy will occur for a general value of the concentration, x, in
the compound Ax B1x . However, for certain values of x, for example x = 14 , 12 , or 43 , the alloy will
be ordered [1]. It is important to note that a disordered alloy possesses a lattice structure. This is in
contrast to an amorphous system, such as a glass, which has no underlying crystal structure.
A method for determining the effect of alloying is to measure the residual resistivity of the compound as a function of the concentration, x. Residual resistivity is defined as the resistivity in the limit
as temperature goes to zero [1]. The resistivity increases as the alloy becomes more disordered and
decreases as the alloy becomes more ordered. Thus, a minimum in the resistivity versus concentration
indicates an ordered alloy. The data by Johansson and Linde [2] on the binary system Cu x Au1x
shows two minima in the resistivity as shown in the figure below.

Figure 1: Resistivity versus atomic percent of gold. The original data and diagram are from Johansson
and Linde. The plot above is from Kittel.
The first minimum occurs at 25% Au and the second minimum occurs at 50% Au. This implies
there are two ordered systems of the form Cu3 Au and CuAu. However, this tells us nothing about
wheather these ordered phases are fcc based structures or some other type of structure. To get this
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information we must look at the Au-Cu phase diagram shown below. This diagram is from Massalski
[3].

Figure 2: Phase diagram for the Au-Cu system.

The phase diagram shows the Cu3 Au phase around 25% Au and the CuAu phase around 50%
Au. There are actually two CuAu phases referred to as CuAu I and CuAu II. There is also a third
phase CuAu3 , which did not show up in the resistivity measurement of Johansson and Linde. This is
probably because the diffusion time for this phase is longer than the other two. Hanson [4] indicates
that the Cu3 Au phase is an fcc based structure. This is referred to as the L12 structure for the Au-Cu
alloy. The CuAu I phase has a tetragonal based structure, referred to as the L1 0 type structure. CuAu
II has an orthorhombic based structure which is closely related to the CuAu I structure [4]. Massalski
[3] indicates that the CuAu3 based structure is L12 . For the problem we are considering here we will
ignore the CuAu3 phase because there are many unanswered questions concerning this phase.
Thus, we see that the Au-Cu system will form an ordred alloy with an fcc based lattice of the form
Cu3 Au (75% Cu and 25% Au) below 400 C. The Au atoms will occupy the 000 position and the Cu
atoms will occupy the 21 21 0, 12 0 21 , and 0 21 12 positions [1].
In order to experimentally determine wheather the alloy is ordered or not we see that we can
get some information from a measure of the residual resistivity. However, a better way is to use the
method of x-ray diffraction. Remember that a disordered alloy possesses a lattice structure, thus, a
disordered alloy will produce sharp x-ray diffraction lines as indicated in the x-ray powder photograph
shown below [1].

Figure 3: X-ray powder photograph for the disordered Cu3 Au alloy. This photograph is from Kittel.
The above x-ray powder photograph for the disordered Cu3 Au alloy is what you would expect if
each lattice site were occupied by only one type of atom. Thus the effective scattering power of each
plane is equal to the average of the Au and Cu scattering powers [1].
An x-ray powder photograph of the ordered Cu3 Au phase shows extra diffraction lines which are
not present in the disorderd phase as shown below [1].

Figure 4: X-ray powder photograph for the ordered Cu3 Au alloy. This photograph is from Kittel.
The extra diffraction lines are referred to as superstructure lines.
As an aside, refer back to the Au-Cu phase diagram.
Beginning at high temperatures and going down the diagram we see that we are, at first, in a
liquid phase. This is indicated by L in the diagram. As we continue down the diagram we come
to two lines which begin just below 1100 C. These lines are phase boundaries. Between the two
lines we have a phase which consists of both a liquid and a solid disordered alloy. This is just like
having a stable ice/water mixture. Continuing down, below 899 C at 56.5% Au, we have only a solid
disordered phase. As we continue down the diagram at around 400 C we encounter the solid ordered
alloy phases of Au-Cu. Here, we see, several phases exist depending on the concentrations of Cu and
Au.
Not indicated in the phase diagram is the behavior of the phase boundary lines for the solid
ordered phases as we continue down in temperature. According to the third law of thermodynamics
the entropy of a system approaches a constant value in the limit as temperature goes to 0 K. Another
way to say this, according to Nernst, is that at 0 K the entropy difference vanishes between all of
the configurations of a system which are in internal thermal equilibrium. See Kittel and Kroemer
[5]. Thus, we would expect the solid phase boundary curves to taper inward as the temperature
approaches 0 K. This is indicated below.

Temperature
0K

Concentration
Figure 5: Behavior of solid ordered alloy phase boundary as temperature decreases.

Ibach and L
uth Problem 2.4

The following solution to this problem can be found in Ashcroft and Mermin [6].
Crystals can be divided into seven crystal systems with fourteen Bravais lattices. These are
described in the table below.

Crystal System
Cubic

Tetragonal
Orthorhombic

Monoclinic
Triclinic
Trigonal
Hexagonal

Bravais Lattice
simple cubic
body-centered cubic
face-centered cubic
simple tetragonal
centered tetragonal
simple orthorhombic
based-centered orthorhombic
body-centered orthorhombic
face-centered orthorhombic
simple monoclinic
centered monoclinic
triclinic
trigonal
hexagonal

A diagram of each crystal structure is shown in the figure below.

Figure 6: The different crystal systems: (a) cubic, (b) tetragonal, (c) orthorhombic, (d) monoclinic,
(e) triclinic, (f) trigonal, (g) hexagonal. This diagram is from Ashcroft and Mermin.

Crystallographic Point Groups

There are 32 crystallographic point groups. These arise from the following symmetry operations.

(1) Rotation through integral multiples of 2

n about some axis.
(2) Rotation - Reflection which consists of a rotation followed by a reflection in a plane perpendicular to
the rotation axis.
(3) Rotation - Inversion which is a rotation followed by an inversion in a point lying on the rotation axis.
(4) Reflection which takes every point into its mirror image in a plane.
(5) Inversion

In what follows, Schoenflies notation will be used to indicate the point groups.

O:
T:
C:
D:
S:
h:
v:
d:
n:

octahedron
full symmetry group of the cube.
tetrahedron
full symmetry group ot teh tetrahedron.
cyclic
dihedral
spiegel
(mirror)
horozontal
vertical
diagonal
n-fold axis

Cn :
Cnv :
Cnh :
Sn :
Dn :
Dnh :
Dnd :
Oh :
Td :
Th :

n-fold rotation axis

n-fold rotation axis plus a mirror plane
n-fold axis plus a single mirror plane perpendicular to the axis
n-fold rotation-reflection axis
n-fold rotation axis plus a 2-fold axis perpendicular to an n-fold axis
Dn plus a mirror plane perpendicular to the n-fold axis
Dn plus mirror planes containing the n-fold axis which bisect the angles between the 2-fold axes
full symmetry group for the cube with improper rotations
full symmetry group of the tetrahedron plus improper rotations
T plus inversion

The 32 point groups are:

Cubic:
Tetragonal:
Orthorhombic:
Monoclinic:
Triclinic:
Trigonal:
Hexagonal:

Oh , O, Th , Td , T
C4 , C4v , C4h , S4 , D4 , D4h , D2d
C2v , D2 , D2h
C2 , C2h , C1h
C 1 , S2
C3 , C3v , S6 , D3 , D3d
C6 , C6v , C6h , C3h , D6 , D6h , D3h

These point groups can be shown diagramatically in the following figures.

Figure 7: The cubic group. This diagram is from Ashcroft and Mermin.

Figure 8: The noncubic groups. This diagram is from Ashcroft and Mermin.

Ibach and L
uth Problem 2.7

Simple Cubic
The simple cubic structure is shown below.

Figure 9: The simple cubic structure (top view).

The radius of each sphere is

a = 2r

r=

a
2

Each corner contains 18 of a sphere, thus, there are 8 81 = 1 sphere in the simple cubic structure.
The volume of the sphere is

1 4 3
4 a 3
4 a3
Vsph = 8
r =
=
8 3
3
2
3 8
3
a
6

Vsph =
The packing fraction is

Vsph
= 63 = = 0.52
f=
Vcube
a
6

Face-Centered Cubic
The face-centered cubic structure is shown below.

r
2r

face diagonal

Figure 10: The face-centered cubic structure (top view).

The face diagonal has a distance of

2 a. The radius of each sphere is

2a
2 a = 4r r =
4

Each corner contains 18 of a sphere and each face contains 21 of a sphere, thus, there are 8
spheres in the face-centered cubic structure. The volume of the spheres is
4
4
4 3
r + (3) r2 = (4) r3
3
3
3
!

3

2a
2a3
4
=4
=
3
4
6

Vsph = (1)

Vsph
The packing fraction is

Vsph
=
f=
Vcube

2a3
6
a3

10

2
= 0.74
6

1
8

+6

1
2

=4

Body-Centered Cubic
The body-centered cubic structure is shown below.

r
2r

body diagonal

Figure 11: The body-centered cubic structure (top view).

3 a. The radius of each sphere is

3a
3 a = 4r r =
4

The body diagonal has a distance of

corner contains 18 of a sphere and the cube contains one whole sphere, therefore, there are
1Each

8 8 + 1 = 2 spheres in the body-centered cubic structure. The volume of the spheres is

4
4
4 3
r + (1) r3 = (2) r3
3
3
3

3

4
3a
3a3
=2
=
3
4
8

Vsph = (1)

Vsph
The packing fraction is

Vsph
=
f=
Vcube

3a3
8
a3

11

3
= 0.68
8

Diamond
The diamond structure is shown below. Note that the spheres are not to scale in order to make
the diagram easier to see.

r
2r

body diagonal
2r
2r
r

Figure 12: The diamond structure (top view).

The body diagonal has a distance of

3 a. The radius of each sphere is

3a
3 a = 8r r =
8

1
Each corner contains 81 of a sphere,
1 each
1 face contains 2 of a sphere and the cube contains 4 whole
spheres, therefore, there are 8 8 + 6 2 + 4 = 8 spheres in the diamond structure. The volume of
the spheres is

!3

4
3a
3a3
4 3
r =8
Vsph = 8
=
3
3
8
16

The packing fraction is

Vsph
f=
=
Vcube

3a3
16
a3

12

3
= 0.34
16

Hexagonal Close-Packed
The hexagonal close-packed structure is shown below.

r
2r

a
r

Figure 13: The hexagonal close-packed structure (top view).

Each diagonal has a distance of 2a. The radius of sphere is

a
2a = 4r r =
2
1
Each corner contains 61 of a sphere and the top and bottom faces each
1 contain
1 2 of a sphere. The
hexagonal structure also contains 3 whole spheres, thus, there are 12 6 + 2 2 + 3 = 6 spheres in
the hexagonal close-packed structure. The volume of the spheres is

a 3
4
Vsph = 6
r3 = 8
= a3
3
2

The volume of the hexagonal structure is Vhex = cArea. Where c is the height of the hexagonal
structure as shown in the figure below.

Figure 14: Definition of c for the hexagonal close-packed structure. This diagram is from Ahcroft and
Mermin.

The Area of each face is given by

3 3
6 2
=
a2
Area = a cot
4
6
2
Thus, the volume of the hexagonal structure is

3 3 2
Vhex =
ca
2
13

Now, using
c
=
a
we can rewrite the voulme as
Vhex

8
3

c=

3 3 2 8
a
a = 3 2 a3
=
2
3

The packing fraction is

f=

8
a
3

Vsph
a3

=
= =
Vhex
3 2a3
3 2

2
= 0.74
6

Note that the hcp structure has the same packing fraction as the fcc structure. This is because
both the hcp and fcc structures yield the maximum packing factor for hard spheres [1].

14

Ibach and L
uth Problem 2.8

Derivation of the two-dimensional rotation matrix.

Figure 15: Rotated coordinate system.

From the diagram above we can immediately see that

x0
y0

=
=

x cos + y sin
x sin + y cos

This can be written in matrix form as

0
cos
x
=
y0
sin
Thus the rotation matrix is
R=
An n-fold rotation implies =
2-fold: =

2
2

sin
cos

2
n .

=
R=

3-fold: =

cos
sin

sin
cos

1
0

0
1

2
3

R=

21
23

15

3
2
21

x
y

4-fold: =

2
4

R=

6-fold: =

2
6

0
1

1
0

R=

1
2
23

3
2
1
2

Tinkham [7] defines a reducible matrix as one that can be put in block diagonal form. The 2-fold
rotation matrix is already in block diagonal form and is, therefore, reduced.
The 3-fold rotationmatrix can
be diagonalized by finding the eigenvalues and eigenvectors. The
1
3
eigenvalues are = 2 i 2 which are complex, thus, we have not reduced the dimension of the
matrix. Therefore, the 3-fold rotation matrix is irreducible.
The 4-fold rotation matrix can also be diagonalized with eigenvalues = i. However, we have
not reduced the dimensionality. Therefore, the 4-fold rotation matrix is not reducible.
Using the same argument for the 6-fold rotation matrix as for the 3-fold we find that the 6-fold
matrix is irreducible.
Thus, only the 2-fold rotation matrix is reducible.

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References
[1] Kittel, Charles. Introduction to Solid State Physics. New York: John Wiley & Sons, 1986.
[2] Johansson, C. H. and J. O. Linde, Annalen Der Physik, 78, 1925, 439-460.
[3] Massalski, Thaddeus B. Binary Alloy Phase Diagrams. American Society for Metals, 1986.
[4] Hanson, Max. Constitution of Binary Alloys. New York: McGraw-Hill, 1958.
[5] Kittel, Charles and Herbert Kroemer. Thermal Physics. San Francisco: W. H. Freeman and Co.,
1980.
[6] Ashcroft, Neil W. and N. David Mermin. Solid State Physics. Philadelphia: W. B. Saunders Co.,
1976.
[7] Tinkham, Michael. Group Theory and Quantum Mechanics. New York: McGraw-Hill, 1964.

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