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Electrons in Metals: Free Electron Model

Electrons in metals can be modeled as a free electron gas where valence electrons are delocalized and move freely through the crystal lattice. This model describes many important properties of metals despite being a simplification. It assumes electrons interact with a uniform positive background of ion cores but not with each other. The electrons occupy quantum energy levels according to the Pauli exclusion principle. As temperature increases, the Fermi-Dirac distribution describes electrons occupying higher energy levels above the Fermi energy level.

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Sofeah Fatima
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168 views12 pages

Electrons in Metals: Free Electron Model

Electrons in metals can be modeled as a free electron gas where valence electrons are delocalized and move freely through the crystal lattice. This model describes many important properties of metals despite being a simplification. It assumes electrons interact with a uniform positive background of ion cores but not with each other. The electrons occupy quantum energy levels according to the Pauli exclusion principle. As temperature increases, the Fermi-Dirac distribution describes electrons occupying higher energy levels above the Fermi energy level.

Uploaded by

Sofeah Fatima
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Electrons in metals: free electron model

• Simplest way to represent the electronic structure of metals


• Although great simplification, works pretty well in many cases, describes
many important properties of metals
• In this model, the valence electrons of free atoms become conduction
electrons in crystal and travel freely
• Neglect the interaction of conduction electrons with ions of the lattice and
the interaction between the conduction electrons – a free electron gas
• Fundamental difference between the free electron gas and ordinary gas of
molecules:
1) electrons are charged particles ⇒ to maintain the charge neutrality of
the whole crystal, we need to include positive ions.
This is done within the jelly model : the positive charge of ions is smeared
out uniformly throughout the crystal - charge neutrality is maintained,
no field on the electrons exerted
2) Free electron gas must satisfy the Pauli exclusion principle, which
leads to important consequences.
Free electron gas in one dimension
Assume an electron of mass m is confined to a length L by infinite barriers
Schrödinger equation for electron wave function ψn(x):
En - the energy of electron orbital
assume the potential lies at zero ⇒ H includes only the kinetic energy ⇒

Note: this is a one-electron equation –


neglected electron-electron interactions
General solution: Asin qnx + Bcos qnx
boundary conditions for the wave function:
⇒ B = 0; qn = πn/L ; n - integer
Substitute, obtain
the eigenvalues:
™What is Hamiltonian?
First three energy levels and wave-functions of a free electron
of mass m confined to a line of length L:

picture from Kittel


Fermi energy
We need to accommodate N valence electrons in these quantum states.
Pauli principle: no two electrons can have identical quantum numbers.
Electronic state in a 1D solid is characterized by quantum numbers n
and ms, where n describes the orbital ψn(x), and ms - the projection of
the spin: ms = ±½.
⇒ each orbital labeled by the quantum number n can accommodate
two electrons, one with spin up and one with spin down orientation.

Let nF - the highest filled energy level. Start filling the levels from the
bottom (n = 1) and continue until all N electrons are accommodated.
Condition 2nF = N determines nF
The energy of the highest occupied level is called the Fermi energy EF

For the one-dimensional system of N electrons


Finite temperature: the Fermi - Dirac distribution

The ground state of the N electron system


at zero temperature: all the electronic
levels are filled up to the Fermi energy.
All the levels above are empty.

What happens if the temperature is increased?


The kinetic energy of the electron gas increases with temperature
⇒ some energy levels become occupied which were vacant at 0 K;
some levels become vacant which were occupied at 0 K.
The distribution of electrons among the levels is described by the
distribution function, f(E) - the probability that the level E is occupied
1
Fermi - Dirac distribution: f (E) = ( E − µ ) k BT
e +1
f(E) at T = 0 K and T> 0 K
1
f (E) =
e ( E − µ ) k BT + 1
µ − the chemical potential.
It can be determined in a way that
the total number of electrons in the
system is equal to N.
At T = 0 K µ = EF

At any T if f(E) = 1/2 when E = µ

High energy tail of f(E), when E - µ >> kBT: f ( E ) = e ( µ − E ) k BT


called Maxwell – Boltzmann distribution
Effect of temperature on Fermi-Dirac distribution
Free electron gas in three dimensions
The Schrödinger equation in the three dimensions:

If the electrons are confined to a cube of edge L, the solution is

introduce periodic boundary conditions, as we did for lattice vibrations


– assume that our crystal is infinite and disregard the influence of the
outer boundaries of the crystal on the solution
– require that our wave function is periodic in x, y, and z directions with
period L, so that

and similarly for the y and z coordinates.


The solution of the Schrödinger equation satisfying these boundary
conditions has the form of the traveling plane wave:

ψ k (r ) = Aeik ⋅r
provided that the component of the wave vector k satisfy

where nx, ny, and nz - integers

substitute this to the Schrödinger equation, obtain the energy of the


orbital with the wavevector k:

Wave functions ψk – the eigenfunctions of the momentum operator


p = −i=∇ The eigenvalue of the momentum is ħk.
The velocity of the electron is defined by v = p/m = ħk/m
EF / k B

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