Exercises for Solid State Physics

Class K69 – Second semester 2021/22

Assoc. Prof. Dr. Luc Huy Hoang
Assoc. Prof. Dr. Pham Van Hai

Chapter 1: Bonding in Solids and Crystal Lattices

(Part 1.1)

Theoretical summary:

• One-electron atom: An one-electron atom contains two particles, a positively charged

nucleus and the negatively charged electron. In quantum mechanics, the Schrödinger
equation for one-electron atom gives a set of certain discrete values of the total energy
and function wave. The total energy of the electron depends only on principal quan-
tum number n, whereas the wave function is a function of n, the azimuthal quantum
number l, the magnetic quantum number ml , and spin quantum number s.
• Multi-electron atoms: A multi-electron atom consists of a nucleus of a charge of +Ze
and Z electrons each of charge −e. Therefore, the total energy also depends on Z.
Pauli exclusion must be included when considering the symmetry of the wave function.
• Ionic bonds: An ionic bond is formed through the transfer of one or more electrons of
one atom to another atom.
• Electronegativity: The electronegativity is the ability of an atom to attract electrons
towards itself.
• Covalent bonds: A covalent bon is formed through the sharing of a pair of electrons
between two atoms.
• Molecular orbitals: A molecular orbital is a combination of atomic orbitals. The bond-
ing, antibonding, and nonbonding moleculars are three different kinds of molecular
orbitals.
• Metallic bonds: Metallic bonds are due to the sharing of valence electrons among the
positively-charged ions in the entire crystal.
• Van der Waals bonds: A van der Waals bond is formed through the electron correlation
between two atoms or between two molecules.
• Hydrogen bonds: A hydrogen bond is a chemical bond between atomic hydrogen and
a strongly electronegative atom.
• Valence electrons: The valence electron(s) of an atom participate(s) in the bonding of
the atom with other atoms.
• Metals: Metals are crystals with itinerant valence electrons.
• Insulators: Insulators are crystals with localized valence electrons. Insulators are
classified into: ionic crystals, covelent crystals, molecular crystals, hydrogen-bonded
crystals.
Exercise 1: Van der Waals in a diatomic molecule

Consider a diatomic molecule due to the van der Waals bond with an interaction potential
between a pair of two atoms given by
  
σ 12  σ 6
U (r) = 4ϵ − (1)
r r

where ϵ is the depth of the potential well, σ is the finite distance at which the inter-particle
potential is zero, r is the distance between the atoms (see Figure 1)

a) Show that the equilibrium separation is given by rm = 21/6 σ.

b) Find the strength of the van der Waals bond in the molecules.

Figure 1: A graph of strength versus distance for the 12-6 potential

Exercise 2: Bonding in a three-dimensional ionic crystal

The total energy of a three-dimensional ionic crystal is given by

N A N αZ 2 e2
V (r) = − , (2)
R12 4πϵ0 R

where N is the number of ion pairs and R the nearest-neighbor distance.

a) Derive an expression for the equilibrium value of the nearest-neighbor distance.
b) Compute the binding energy per ion pair in equilibrium.

Exercise 3: Bonding in a three-dimensional crystal

The interparticle interactions as a function of distance is given by:

α β
U (r) = − + 8 (3)
r r
where α, β are constants. Prove that
a) The equilibrium separation is given by
 1/7
8β
r = r0 = (4)
α

b) At the equilibrium separation, the attractive energy is eight times larger than the
repulsive energy.
c) At the equilibrium separation the total energy is determined by
1/7
α8

7 7 α
Utot (r0 ) = − =− × (5)
8 8β 8 r0

d) Find the separation at which the bonding between two particles is broken.

Exercise 4: Madelung constant for one-dimension chain

Consider a one-dimensional chain of alternating positive and negative ions. Show that the
potential energy of an ion in this hypothetical crystal is

e2
U (r) = −kα (6)
r

where α = 2 ln 2 (the Madelung constant), and r is the interionic spacing.

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