A Particle in a Box

• In this section position and momentum probability densities of a system are calculated
considering one of the simplest systems in quantum mechanics:
• a particle of mass 𝑚𝑚 confined in a one dimensional region 0 ≤ 𝑥𝑥 ≤ 𝑎𝑎.
• Such a particle in a state with quantum number 𝑛𝑛 has an energy given by
2
ℏ2 𝑘𝑘𝑛𝑛 𝑛𝑛𝑛𝑛
𝐸𝐸𝑛𝑛 = , with 𝑘𝑘𝑛𝑛 = ,
2𝑚𝑚 𝑎𝑎
• and a wavefunction
𝑁𝑁 sin 𝑘𝑘 −𝑖𝑖𝐸𝐸𝑛𝑛 𝑡𝑡/ℏ
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = � 𝑛𝑛 𝑥𝑥𝑒𝑒 0 < 𝑥𝑥 < 𝑎𝑎.
0 elsewhere
• The normalization constant 𝑁𝑁 can be obtained by normalizing the position probability density.
• This is given by 𝜓𝜓(𝑥𝑥, 𝑡𝑡) 2 ; this is zero outside the region 0 < 𝑥𝑥 < 𝑎𝑎, and inside this region it is
given by
𝑖𝑖𝐸𝐸𝑛𝑛 𝑡𝑡 𝑖𝑖𝐸𝐸𝑛𝑛 𝑡𝑡
2 ∗ + �ℏ − �ℏ
𝜓𝜓(𝑥𝑥, 𝑡𝑡) = 𝑁𝑁 sin 𝑘𝑘𝑛𝑛 𝑥𝑥𝑒𝑒 𝑁𝑁 sin 𝑘𝑘𝑛𝑛 𝑥𝑥 𝑒𝑒 = 𝑁𝑁 2 sin2 𝑘𝑘𝑛𝑛 𝑥𝑥.
• The total probability of finding a particle at any of its possible locations is given by the
normalization integral
+∞ 𝑎𝑎 𝑎𝑎
∫−∞ 𝜓𝜓(𝑥𝑥, 𝑡𝑡) 2 𝑑𝑑𝑑𝑑 = 𝑁𝑁 2 ∫0 sin2 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 = 𝑁𝑁 2 .
2
• By equating this probability to one,
2
• 𝑁𝑁 = give rise to a normalized probability density and to a normalized
𝑎𝑎
wavefunction.
2
�
• The momentum probability density is given by 𝜓𝜓𝑛𝑛 (𝑝𝑝, 𝑡𝑡) , where according
to the momentum probability amplitude
1 +∞
�
𝜓𝜓𝑛𝑛 𝑝𝑝, 𝑡𝑡 = ∫ 𝜓𝜓𝑛𝑛 (𝑥𝑥, 𝑡𝑡) 𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖/ℏ 𝑑𝑑𝑑𝑑.
2𝜋𝜋𝜋 −∞
−𝑖𝑖𝐸𝐸𝑛𝑛 𝑡𝑡/ℏ
• Considering 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = � 𝑁𝑁 sin 𝑘𝑘 𝑛𝑛 𝑥𝑥𝑒𝑒 0 < 𝑥𝑥 < 𝑎𝑎, with , 𝑁𝑁 = 2
,
0 elsewhere 𝑎𝑎
1 +∞ −𝑖𝑖𝑖𝑖𝑖𝑖/ℏ
�
𝜓𝜓𝑛𝑛 𝑝𝑝, 𝑡𝑡 = 𝑒𝑒 −𝑖𝑖𝐸𝐸 𝑛𝑛 𝑡𝑡/ℏ
∫−∞ 𝑒𝑒 sin 𝑘𝑘𝑛𝑛 𝑥𝑥 𝑑𝑑𝑑𝑑,
𝜋𝜋𝜋𝜋𝜋
• and the integral can be easily evaluated using
𝑒𝑒 𝑖𝑖𝑘𝑘𝑛𝑛 𝑥𝑥 −𝑒𝑒 −𝑖𝑖𝑘𝑘𝑛𝑛 𝑥𝑥
sin 𝑘𝑘𝑛𝑛 𝑥𝑥 = .
2𝑖𝑖
Position and momentum probability densities for a particle enclosed in a box (0 < x < a)
Operators Expectation values
• every measurable physical quantity has a • for an operator 𝐴𝐴̂ the expectation value is:
corresponding operator.
• Observables in quantum mechanics are 𝐴𝐴̂ = � ̂ 3 𝑟𝑟
Ψ ∗ 𝐴𝐴Ψ𝑑𝑑
described by operators. all space
• The result of a measurement yields one of expectation value of position:
the eigenvalues 𝜒𝜒𝑛𝑛 of the corresponding
operator.
𝑟𝑟⃗ = � Ψ ∗ 𝑟𝑟Ψ𝑑𝑑
⃗ 3 𝑟𝑟
• Explicit operators:
all space
position operator: 𝑟𝑟⃗ = (𝑥𝑥, 𝑦𝑦, 𝑧𝑧) expectation value of momentum:

momentum operator: 𝑝𝑝⃗̂ = −𝑖𝑖ℏ𝛻𝛻 𝑝𝑝⃗̂ = � Ψ ∗ 𝑝𝑝Ψ𝑑𝑑

⃗ 3 𝑟𝑟
𝜕𝜕 𝜕𝜕 𝜕𝜕 all space
= 𝑖𝑖ℏ , ,
𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕
total energy:𝐸𝐸� = 𝑖𝑖ℏ
𝜕𝜕 = � Ψ ∗ − 𝑖𝑖ℏ𝛻𝛻Ψ𝑑𝑑3 𝑟𝑟
𝜕𝜕𝜕𝜕
all space
Bra – ket notation or Dirac’s notation
 the ket | ⟩ represent a system in an initial state
 the bra ⟨ | represent a system in a final state
 e.g. 𝑥𝑥 = 0.5 𝜓𝜓 is the probability amplitude that a particle in state 𝜓𝜓 will be
found at position 𝑥𝑥 = 0.5
 for the ground state of a particle-in-a-box of unit dimension:
𝑥𝑥 𝜓𝜓 = 𝜓𝜓 𝑥𝑥 = 2 sin(𝜋𝜋𝜋𝜋)
 so is the bra – ket pair
 and | ⟩⟨ | is the ket – bra product
 for discrete basis states: ∑𝑛𝑛|𝑛𝑛⟩⟨𝑛𝑛| = 1
 for continuous basis states: ∫|𝑥𝑥⟩⟨𝑥𝑥|𝑑𝑑𝑑𝑑 = 1
 applying the bra-ket notation
𝜓𝜓 𝜓𝜓 = � 𝜓𝜓 𝑥𝑥 𝑥𝑥 𝜓𝜓 𝑑𝑑𝑑𝑑 = � 𝜓𝜓 ∗ 𝑥𝑥 𝜓𝜓 𝑥𝑥 𝑑𝑑𝑑𝑑

Φ Ψ = � Φ 𝑥𝑥 𝑥𝑥 Ψ 𝑑𝑑𝑑𝑑 = � Φ∗ (𝑥𝑥) Ψ(𝑥𝑥) 𝑑𝑑𝑑𝑑

A position wave function is defined by 𝜓𝜓 𝑥𝑥 = 𝐴𝐴𝐴𝐴 in the region −1 ≤ 𝑥𝑥 ≤ 1 .
3.2.1 Normalise the wave function in order to obtain the value of the
constant 𝐴𝐴.
3.2.2 Compute 𝑥𝑥� .
3.2.3 Compute 𝑝𝑝̂ .

3.2.1 Normalise the wavefunction in order to obtain the value of the constant A.
+1 + +1
3
𝑥𝑥 1 − (−1) 2
� 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 = 𝐴𝐴2 � 𝑥𝑥 2 𝑑𝑑𝑑𝑑 = 𝐴𝐴2 � = 𝐴𝐴2 2
= 𝐴𝐴 = 1
3 3 3
−1 −1 −1

3
⟹ 𝐴𝐴 =
2
3.2.2 Compute 𝑥𝑥�
+1 +1 +1
3 3 3 3 𝑥𝑥 4 3 1−1
𝑥𝑥� = � 𝑥𝑥 𝑥𝑥 3
𝑥𝑥 𝑑𝑑𝑑𝑑 = � 𝑥𝑥 𝑑𝑑𝑑𝑑 = = =0
2 2 2 2 4 −1
2 4
−1 −1
+1
2 +1 3 3 3 +1 4 3 𝑥𝑥 5 3 1+1 3
𝑥𝑥� = ∫−1 𝑥𝑥 𝑥𝑥 2 𝑥𝑥𝑥𝑥𝑥𝑥 = ∫−1
𝑥𝑥 𝑑𝑑𝑑𝑑 = = =
2 2 2 2 5 −1 2 5 5

3.2.3 Compute 𝑝𝑝̂

+1 3 𝑑𝑑 3 3 +1 𝑑𝑑
𝑝𝑝̂ = ∫−1 𝑥𝑥 − 𝑖𝑖𝑖 𝑥𝑥 𝑑𝑑𝑑𝑑 = −𝑖𝑖𝑖 ∫−1 𝑥𝑥 𝑑𝑑𝑑𝑑 𝑥𝑥𝑥𝑥𝑥𝑥 =
2 𝑑𝑑𝑑𝑑 2 2
+1
3 +1 3 𝑥𝑥 2
−𝑖𝑖𝑖 ∫−1 𝑥𝑥𝑥𝑥𝑥𝑥 = −𝑖𝑖𝑖 =0
2 2 2 −1
Particle in a Box II
• Consider a particle in a one dimensional box of dimension 0 ≤ 𝑥𝑥 ≤ 𝑎𝑎
• Its potential is defined by

0 0 ≤ 𝑥𝑥 ≤ 𝑎𝑎
𝑉𝑉 𝑥𝑥 = ,
∞ elsewhere

• This is an infinite potential well which confines a particle in a one dimensional box of
size 𝑎𝑎.
• Classically, the particle is either lying down the well with zero energy or it is
bouncing back and forth between the walls of the well with energy up to infinity.
• In quantum mechanics more varied and quantized states of the particle exist.
• Their wavefunctions are defined by the one dimensional Schrödinger equation
𝜕𝜕 ℏ2 𝑑𝑑 2
𝑖𝑖𝑖 Ψ 𝑥𝑥, 𝑡𝑡 = − + 𝑉𝑉(𝑥𝑥) Ψ(𝑥𝑥, 𝑡𝑡).
𝜕𝜕𝜕𝜕 2𝑚𝑚 𝑑𝑑𝑑𝑑 2
• If the particle has a definite energy 𝐸𝐸𝑛𝑛 then the wavefunction has the form
𝐸𝐸
−𝑖𝑖 ℏ𝑛𝑛 𝑡𝑡
Ψ 𝑥𝑥, 𝑡𝑡 = 𝜓𝜓(𝑥𝑥)𝑒𝑒 ,
• The wavefunction 𝜓𝜓(𝑥𝑥) satisfy the energy eigenvalue equation
ℏ2 𝑑𝑑 2
𝐸𝐸𝐸𝐸 𝑥𝑥 = − + 𝑉𝑉 𝑥𝑥 𝜓𝜓(𝑥𝑥),
2𝑚𝑚 𝑑𝑑𝑑𝑑 2
• This is often referred to as the time-independent Schrödinger equation or steady-state
Schrödinger equation .
• The task now is to find the physically acceptable solutions to the above equation.
• Because the potential rises abruptly to infinity at 𝑥𝑥 = 0 and 𝑥𝑥 = 𝑎𝑎, particle is strictly
confined in the region 0 ≤ 𝑥𝑥 ≤ 𝑎𝑎,
• Beyond this region the eigenfunction 𝜓𝜓(𝑥𝑥) is zero!
• Inside this region, the potential energy is zero, so the eigenfunction is a solution of the
Schrödinger equation with 𝑉𝑉 𝑥𝑥 = 0.
• This equation is simplified by writing the energy as
ℏ2 𝑘𝑘 2
𝐸𝐸 = ,
2𝑚𝑚

• so that the Schrödinger equation can now appear as

𝑑𝑑 2
𝜓𝜓 𝑥𝑥 = −𝑘𝑘 2 𝜓𝜓(𝑥𝑥).
𝑑𝑑𝑑𝑑 2
• Physically acceptable solutions to this partial differential equation are
obtained from the general solution
𝜓𝜓 𝑥𝑥 = 𝑀𝑀 cos 𝑘𝑘𝑘𝑘 + 𝑁𝑁 sin 𝑘𝑘𝑘𝑘,
• 𝑀𝑀 and 𝑁𝑁 are constants.
• The imposed boundary conditions are
𝜓𝜓 0 = 𝜓𝜓 𝑎𝑎 = 0

• This is to ensure that the position probability of the particle does not change
abruptly at the edges.
• It must be noted the eigenvalue problem of a particle in a one dimensional
box is identical to the eigenvalue problem of a vibrating string.
• In both cases there are infinite number of eigenfunctions identified by an
integer 𝑛𝑛 = 1, 2, 3, … .
• They are given by
𝑛𝑛𝑛𝑛
𝜓𝜓𝑛𝑛 𝑥𝑥 = 𝑁𝑁 sin 𝑘𝑘𝑛𝑛 𝑥𝑥, and 𝑘𝑘𝑛𝑛 = ,
𝑎𝑎
• where 𝑁𝑁 is an arbitrary constant, and they are illustrated below.
• In classical physics, eigenfunctions 𝜓𝜓𝑛𝑛 are used to describe the possible shapes of normal
modes of vibration of a string.
• In quantum mechanics they can be used to describe possible shapes of wavefunctions of a
particle in a box with definite energies 𝐸𝐸𝑛𝑛 , associated with quantum numbers 𝑛𝑛 = 1, 2, 3, … .
• In conclusion the possible energy levels of a particle in a one dimensional box with width 𝑎𝑎 are
given by
𝑛𝑛2 𝜋𝜋2 ℏ2
𝐸𝐸𝑛𝑛 = ,
with 𝑛𝑛 = 1, 2, 3, …,
2𝑚𝑚𝑎𝑎2
• and that a particle with energy 𝐸𝐸𝑛𝑛 , has a wavefunction of the form
𝐸𝐸
−𝑖𝑖 ℏ𝑛𝑛 𝑡𝑡
Ψ 𝑥𝑥, 𝑡𝑡 = 𝑁𝑁 sin 𝑘𝑘𝑛𝑛 𝑥𝑥 𝑒𝑒 .
Note the following:
𝐸𝐸 −𝐸𝐸 2
• The separation between energy levels 𝑛𝑛+1 𝑛𝑛 ⟶ increases with increasing quantum
𝐸𝐸𝑛𝑛 𝑛𝑛
number 𝑛𝑛.
𝜋𝜋2 ℏ2
• The minimum energy state is not zero but some minimum value 𝐸𝐸1 = .
2𝑚𝑚𝑎𝑎2
• The spacial shape of the wavefunction of a particle in box with energy 𝐸𝐸 is identical to the
spacial shape of the normal modes of a vibrating string with angular frequency 𝜔𝜔.
• The wavefunction of a particle in a box, unlike the displacement of a vibrating string is not an
observable quantity.
• But it can be used to construct physical observables like position and momentum.
Square-well potential
• How quantum particles can be bound or scattered by potential energy fields
can be explained by using the models of square wells and square barriers.
• Here Schrödinger equation can be solved easily using elementary
mathematics.
• The possible energies of a particle can be found and the properties of the
wavefunction are self-evident.
• Here quantum states of a particle in a one dimensional square-well potential
are considered.
• It will be shown that when the well is deep enough, bound states with discrete
energy levels are possible.
• Consider a particle of mass 𝑚𝑚 in a one dimensional potential defined by
∞ if − ∞ ≤ 𝑥𝑥 ≤ 0
• 𝑉𝑉 𝑥𝑥 = � −𝑉𝑉0 if 0 ≤ 𝑥𝑥 ≤ 𝑎𝑎 .
0 if 𝑎𝑎 ≤ 𝑥𝑥 ≤ +∞
• The potential energy changes abruptly at 𝑥𝑥 = 0 and 𝑥𝑥 = 𝑎𝑎.
• There is a potential well of depth 𝑉𝑉0 , which may or may not trap the particle,
and an infinite wall at 𝑥𝑥 = 0 which repels the particle.
A Square-well potential model
• In this situation classically, the energy of the particle is given by the sum
of the kinetic energy and potential energy:
𝑝𝑝2
𝐸𝐸 = 𝐾𝐾 + 𝑉𝑉 𝑥𝑥 = + 𝑉𝑉(𝑥𝑥).
2𝑚𝑚

• The particle is said to be bound or trapped in a well of depth −𝑉𝑉0 ,

• Its energy is negative in the region −𝑉𝑉0 ≤ 𝐸𝐸 ≤ 0.
• Here, the particle bounces back and forth between 𝑥𝑥 = 0 and 𝑥𝑥 = 𝑎𝑎,
with kinetic energy given by 𝐾𝐾 = 𝐸𝐸 + 𝑉𝑉0 .
• But when the energy is positive, the particle is unbound.
• For example, it can approach the well from 𝑥𝑥 = +∞ with kinetic
energy 𝐾𝐾 = 𝐸𝐸,
• At 𝑥𝑥 = 𝑎𝑎 kinetic energy rises to 𝐾𝐾 = 𝐸𝐸 + 𝑉𝑉0 , it hits the infinitely high
potential wall at 𝑥𝑥 = 0, then bounces back to 𝑥𝑥 = +∞.
• In quantum mechanics, the particles motion is described by the wavefunction
Ψ(𝑥𝑥, 𝑡𝑡) which is a solution of the Schrödinger wave equation
𝜕𝜕 ℏ2 𝑑𝑑 2
𝑖𝑖𝑖 Ψ 𝑥𝑥, 𝑡𝑡 = − + 𝑉𝑉(𝑥𝑥) Ψ(𝑥𝑥, 𝑡𝑡).
𝜕𝜕𝜕𝜕 2𝑚𝑚 𝑑𝑑𝑑𝑑 2

• If the particle has definite energy 𝐸𝐸, the wavefunction takes the form
−𝑖𝑖 𝐸𝐸� 𝑡𝑡
• Ψ 𝑥𝑥, 𝑡𝑡 = 𝜓𝜓(𝑥𝑥)𝑒𝑒 ℏ ,

• where 𝜓𝜓(𝑥𝑥) is the eigenfunction which satisfy the energy eigenvalue equation
ℏ2 𝑑𝑑 2
− 𝜓𝜓(𝑥𝑥) + 𝑉𝑉 𝑥𝑥 𝜓𝜓 𝑥𝑥 = 𝐸𝐸𝐸𝐸(𝑥𝑥).
2𝑚𝑚 𝑑𝑑𝑑𝑑 2

• After solving this energy eigenvalue equation for suitable eigenvalues and
eigenfunctions, any quantum states of the particle in a potential can be written
as the linear superposition of energy eigenfunctions.
Bound states
• If a bound state exists, it has a negative energy somewhere between 𝐸𝐸 = −𝑉𝑉0 and 𝐸𝐸 =
0.
• Let 𝐸𝐸 = −𝜖𝜖, where 𝜖𝜖 is the particles binding energy, and seek the solutions to time-
independent SE above.
In the region −∞ ≤ 𝑥𝑥 ≤ 0
• The potential energy is infinite, so the only possible solution to equation SE is 𝜓𝜓 𝑥𝑥 = 0,
which means the particle will never be found in the negative 𝑥𝑥 direction.
In the region 0 ≤ 𝑥𝑥 ≤ 𝑎𝑎
• The potential energy is 𝑉𝑉 𝑥𝑥 = −𝑉𝑉0 and SE equation has the form
𝑑𝑑 2 ℏ2 𝑘𝑘02
𝜓𝜓
𝑥𝑥 = −𝑘𝑘02 𝜓𝜓(𝑥𝑥), with 𝐸𝐸 = − 𝑉𝑉0 .
𝑑𝑑𝑑𝑑 2 2𝑚𝑚
• The general solution to this equation is
𝜓𝜓 𝑥𝑥 = 𝐶𝐶 sin 𝑘𝑘0 𝑥𝑥 + 𝛾𝛾 ,
• where 𝐶𝐶 and 𝛾𝛾 are arbitrary constants. To ensure continuity of 𝜓𝜓(𝑥𝑥) at 𝑥𝑥 = 0, 𝛾𝛾 is set to
zero so that
𝜓𝜓 𝑥𝑥 = 𝐶𝐶 sin 𝑘𝑘0 𝑥𝑥.
In the region 𝑎𝑎 ≥ 𝑥𝑥 ≥ +∞
• The potential energy is zero so the SE equation takes the form
𝑑𝑑 2 2 𝛼𝛼2 ℏ2
𝜓𝜓 𝑥𝑥 = 𝛼𝛼 𝜓𝜓(𝑥𝑥), with 𝐸𝐸 = − .
𝑑𝑑𝑑𝑑 2 2𝑚𝑚
• The general solution is
𝜓𝜓 𝑥𝑥 = 𝐴𝐴𝑒𝑒 −𝛼𝛼𝛼𝛼 + 𝐴𝐴𝐴𝑒𝑒 +𝛼𝛼𝛼𝛼

• For the particle’s wavefunction to be continuous at 𝑥𝑥 = 𝑎𝑎:

𝜓𝜓(𝑥𝑥)𝑉𝑉=−𝑉𝑉0 = 𝜓𝜓(𝑥𝑥)𝑉𝑉=0 𝐶𝐶 sin 𝑘𝑘0 𝑎𝑎 = 𝐴𝐴𝑒𝑒 −𝛼𝛼𝛼𝛼

𝑑𝑑 𝑑𝑑 𝑘𝑘0 𝐶𝐶 cos 𝑘𝑘0 𝑎𝑎 = −𝛼𝛼𝛼𝛼𝑒𝑒 −𝛼𝛼𝛼𝛼

𝜓𝜓(𝑥𝑥)𝑉𝑉=−𝑉𝑉0 = 𝜓𝜓(𝑥𝑥)𝑉𝑉=0
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑
• In order to find the binding energies, it must be noted that 𝑘𝑘0 and 𝛼𝛼 are
not independent parameters.
• These are defined by
ℏ2 𝑘𝑘02 𝛼𝛼2 ℏ2
𝐸𝐸 = − 𝑉𝑉0 , and 𝐸𝐸 = − ,
2𝑚𝑚 2𝑚𝑚
• which imply that
𝑤𝑤 2 ℏ2
𝛼𝛼 2 + 𝑘𝑘02 = 𝑤𝑤 2 , where 𝑤𝑤 is given by 𝑉𝑉0 = .
2𝑚𝑚

• This has results in two simultaneous equations:

𝑘𝑘0 cot 𝑘𝑘0 𝑎𝑎 = −𝛼𝛼 ---------------------(a)
𝛼𝛼 2 + 𝑘𝑘02 = 𝑤𝑤 2 ---------------------(b)
• These equations can be solved graphically by finding the intersection
points of the two curves 𝑘𝑘0 cot 𝑘𝑘0 𝑎𝑎 = −𝛼𝛼 and 𝛼𝛼 2 + 𝑘𝑘02 = 𝑤𝑤 2 .
• The figure shows the number of intersection points, and hence the number of bound
states increase as the potential well becomes deeper!
• Particularly there are no bound states for a shallow well with
𝜋𝜋
𝑤𝑤 < ,
2𝑎𝑎
• there is one bound states when
𝜋𝜋 3𝜋𝜋
< 𝑤𝑤 < ,
2𝑎𝑎 2𝑎𝑎
• there are two bound states when
3𝜋𝜋 5𝜋𝜋
< 𝑤𝑤 < ,
2𝑎𝑎 2𝑎𝑎
• and so on.
• To illustrate the 2𝜋𝜋
nature of bound states, consider a potential with well-depth
parameter 𝑤𝑤 = , which corresponds to well with depth
𝑎𝑎
2𝜋𝜋2 ℏ2
𝑉𝑉0 = .
𝑚𝑚𝑎𝑎2
• In this case two bound states exist, with ground state energy and the first excited state
energy
𝜋𝜋2 ℏ2 𝜋𝜋2 ℏ2
𝜖𝜖1 = 3.26 , and 𝜖𝜖2 = 1.17 .
2𝑚𝑚𝑎𝑎2 2𝑚𝑚𝑎𝑎2
Infinite well potential Square-well potential
• In the regions −∞ ≤ 𝑥𝑥 ≤ 0 and • In the region −∞ ≤ 𝑥𝑥 ≤ 0
𝑎𝑎 ≥ 𝑥𝑥 ≥ +∞ 𝜓𝜓(𝑥𝑥) = 0
𝜓𝜓 𝑥𝑥 = 0 • In the region 0 ≤ 𝑥𝑥 ≤ 𝑎𝑎
• In the region 0 ≤ 𝑥𝑥 ≤ 𝑎𝑎 𝑑𝑑 2
𝑑𝑑 2
SE:− 2 𝜓𝜓 𝑥𝑥 = −𝑘𝑘02 𝜓𝜓(𝑥𝑥), with 𝐸𝐸 =
𝑑𝑑𝑑𝑑
SE: 2 𝜓𝜓 𝑥𝑥 = −𝑘𝑘 2 𝜓𝜓(𝑥𝑥), with 𝐸𝐸 = 2 2
ℏ 𝑘𝑘0
𝑑𝑑𝑑𝑑
ℏ 𝑘𝑘 2
2 − 𝑉𝑉0
2𝑚𝑚
2𝑚𝑚 Solution: 𝜓𝜓 𝑥𝑥 = 𝐶𝐶 sin 𝑘𝑘0 𝑥𝑥
Solution: 𝜓𝜓𝑛𝑛 𝑥𝑥 = 𝑁𝑁 sin 𝑘𝑘𝑛𝑛 𝑥𝑥 • In the region 𝑎𝑎 ≥ 𝑥𝑥 ≥ +∞
𝑑𝑑 2
SE: 2 𝜓𝜓 𝑥𝑥 = 𝛼𝛼 2 𝜓𝜓(𝑥𝑥), with 𝐸𝐸 =
𝑑𝑑𝑑𝑑
𝛼𝛼2 ℏ2
−
2𝑚𝑚
Solution:𝜓𝜓 𝑥𝑥 = 𝐴𝐴𝑒𝑒 −𝛼𝛼𝛼𝛼
Infinite well potential Square-well potential

0 0 ≤ 𝑥𝑥 ≤ 𝑎𝑎 ∞ if − ∞ ≤ 𝑥𝑥 ≤ 0
𝑉𝑉 𝑥𝑥 = � 𝑉𝑉 𝑥𝑥 = � −𝑉𝑉0 if 0 ≤ 𝑥𝑥 ≤ 𝑎𝑎
∞ elsewhere
0 if 𝑎𝑎 ≤ 𝑥𝑥 ≤ +∞
Potential barrier
• Consider a barrier potential field in one dimension defined by
0 if − ∞ ≤ 𝑥𝑥 ≤ 0
𝑉𝑉 𝑥𝑥 = 𝑉𝑉0 if 0 ≤ 𝑥𝑥 ≤ 𝑎𝑎,
0 if 𝑎𝑎 ≤ 𝑥𝑥 ≤ +∞

• This potential can be illustrated as in a figure below

• If the classical particle approaches this step from the left,
• it gets reflected at 𝑥𝑥 = 0 if its energy is less than the potential step 𝑉𝑉0 ,
• it gets transmitted through if its energy is greater than the potential
barrier.
A potential barrier which illustrates quantum tunnelling effect
• Quantum mechanically, if a particle approaches the barrier the result is uncertain.
• The particle may be reflected or transmitted depending on the state of the incident
particle.
• More importantly, it will be shown that even if the energy of a particle is less than the
potential step, the particle may be transmitted through.
• The behaviour of a particle of mass 𝑚𝑚, in a potential barrier 𝑉𝑉(𝑥𝑥) is described by the
Schrödinger equation
𝜕𝜕 ℏ2 𝜕𝜕2
𝑖𝑖𝑖 Ψ 𝑥𝑥, 𝑡𝑡 = − + 𝑉𝑉(𝑥𝑥) Ψ(𝑥𝑥, 𝑡𝑡),
𝜕𝜕𝜕𝜕 2𝑚𝑚 𝜕𝜕𝜕𝜕 2
• In order to describe an uncertain encounter with a barrier, a wavefunction Ψ(𝑥𝑥, 𝑡𝑡)
which describe an incident wave and the probability of being reflected or transmitted
is required.
• This incoming wavefunction must result in an incoming pulse which represent the
probability of an incident wave.
• After hitting the barrier, the wavefunction should give rise in two pulses, one for the
probability that the wavefunction will be reflected, the other for the probability that
wavefunction will be transmitted.
• According to the standard interpretation of the wavefunction, the reflection and
transmission probabilities persist at equal chances until the particle is detected.
Stationary states analysis
• The reflection and transmission probabilities can be calculated by considering
stationary states with definite energy.
• To acquire this, consider a time-independent Schrödinger eigenvalue equation
ℏ2 𝜕𝜕2
𝐸𝐸𝐸𝐸 𝑥𝑥 = − + 𝑉𝑉(𝑥𝑥) 𝜓𝜓(𝑥𝑥).
2𝑚𝑚 𝜕𝜕𝜕𝜕 2

• Due to the simple nature of the barrier potential, it is a straight forward procedure to
find the eigenfunctions which describe the incident, reflected, and transmitted waves.
• The solutions along 𝑥𝑥 at different regions are first sorted out, then joined smoothly at
the boundaries 𝑥𝑥 = 0 and 𝑥𝑥 = 𝑎𝑎.
• On the left hand side of the barrier, the potential 𝑉𝑉 𝑥𝑥 = 0, the eigenfunction 𝜓𝜓(𝑥𝑥)
satisfies the differential equation
𝑑𝑑 2 ℏ2 𝑘𝑘 2
𝜓𝜓 𝑥𝑥 = −𝑘𝑘 2 𝜓𝜓(𝑥𝑥), with 𝐸𝐸 = .
𝑑𝑑𝑑𝑑 2 2𝑚𝑚
2
• The solution representing
2
an incident wave of intensity 𝐴𝐴𝐼𝐼 and reflected wave of
intensity 𝐴𝐴𝑅𝑅 is
𝜓𝜓 𝑥𝑥 = 𝐴𝐴𝐼𝐼 𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖 + 𝐴𝐴𝑅𝑅 𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖 .
• The form of the eigenfunction inside the barrier depends on whether, the energy
of the particle is greater or less than the barrier potential 𝑉𝑉0 .
• If 𝐸𝐸 > 𝑉𝑉0 , the region (0 ≤ 𝑥𝑥 ≤ 𝑎𝑎) is classically allowed and eigenfunctions are
explained by the equation
𝑑𝑑 2 ℏ2 𝑘𝑘02
2 𝜓𝜓 𝑥𝑥 = −𝑘𝑘02 𝜓𝜓(𝑥𝑥), with 𝐸𝐸 = + 𝑉𝑉0 .
𝑑𝑑𝑑𝑑 2𝑚𝑚

• The general solution involves two arbitrary constants and it undulates with wave
number 𝑘𝑘0
𝜓𝜓 𝑥𝑥 = 𝐴𝐴𝑒𝑒 𝑖𝑖𝑘𝑘0 𝑥𝑥 + 𝐴𝐴′𝑒𝑒 −𝑖𝑖𝑘𝑘0 𝑥𝑥 .

• When 𝐸𝐸 < 𝑉𝑉0 , the region (0 ≤ 𝑥𝑥 ≤ 𝑎𝑎) is classically forbidden. The eigenfunctions
are described by the equation
𝑑𝑑 2 ℏ2 𝛽𝛽2
2 𝜓𝜓 𝑥𝑥 = 𝛽𝛽 2 𝜓𝜓(𝑥𝑥), with 𝐸𝐸 = − + 𝑉𝑉0 ,
𝑑𝑑𝑑𝑑 2𝑚𝑚

• and the general solution is

𝜓𝜓 𝑥𝑥 = 𝐵𝐵𝑒𝑒 −𝛽𝛽𝛽𝛽 + 𝐵𝐵′𝑒𝑒 𝛽𝛽𝛽𝛽 .
• Finally, on the right hand side of the barrier the potential energy 𝑉𝑉(𝑥𝑥) = 0.
• The eigenfunctions satisfy the equation on the left hand side and the solution
representing the transmitted wave of intensity 𝐴𝐴 𝑇𝑇 2 is
𝜓𝜓 𝑥𝑥 = 𝐴𝐴 𝑇𝑇 𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖 .

• Smooth joining of these solutions at 𝑥𝑥 = 0 and 𝑥𝑥 = 𝑎𝑎 helps in evaluation of

intensities of reflection and transmission waves.
• Particularly, the expressions for the ratios can be derived:
𝐴𝐴𝑅𝑅 2 𝐴𝐴𝑇𝑇 2
𝑅𝑅 =
𝐴𝐴𝐼𝐼 2 and 𝑇𝑇 = 𝐴𝐴𝐼𝐼 2,

• Because the probability of finding a particle at 𝑥𝑥 is proportional to 𝜓𝜓(𝑥𝑥) 2 , these

ratios are probabilities:
• 𝑅𝑅 is the probability that the particle is reflected and 𝑇𝑇 is the probability that the
particle is transmitted, and sum of these probabilities is one, i.e.
𝑅𝑅 + 𝑇𝑇 = 1.
Tunnelling through the barrier
• The eigenfunction of a particle with 𝐸𝐸 < 𝑉𝑉0 are given by
𝐴𝐴𝐼𝐼 𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖 + 𝐴𝐴𝑅𝑅 𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖 − ∞ ≤ 𝑥𝑥 ≤ 0
𝜓𝜓 𝑥𝑥 = 𝐵𝐵𝑒𝑒 −𝛽𝛽𝛽𝛽 + 𝐵𝐵′ 𝑒𝑒 𝛽𝛽𝛽𝛽 0 ≤ 𝑥𝑥 ≤ 𝑎𝑎 ,
𝐴𝐴 𝑇𝑇 𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖 𝑎𝑎 ≤ 𝑥𝑥 ≤ +∞
• With constants 𝐴𝐴𝐼𝐼 , 𝐴𝐴𝑅𝑅 , 𝐴𝐴 𝑇𝑇 , 𝐵𝐵, and 𝐵𝐵′ having values ensuring 𝜓𝜓(𝑥𝑥) and its derivative
with respect to position are continuous at 𝑥𝑥 = 0 and 𝑥𝑥 = 𝑎𝑎.
𝑑𝑑
• For the 𝜓𝜓(𝑥𝑥) and 𝜓𝜓(𝑥𝑥) to be continuous at 𝑥𝑥 = 0, it require that
𝑑𝑑𝑑𝑑
𝐴𝐴𝐼𝐼 + 𝐴𝐴𝑅𝑅 = 𝐵𝐵 + 𝐵𝐵′,
𝑖𝑖𝑖𝑖𝐴𝐴𝐼𝐼 − 𝑖𝑖𝑖𝑖𝐴𝐴𝑅𝑅 = −𝛽𝛽𝛽𝛽 + 𝛽𝛽𝛽𝛽′,
• and at 𝑥𝑥 = 𝑎𝑎
𝐵𝐵𝑒𝑒 𝛽𝛽𝑎𝑎 + 𝐵𝐵′ 𝑒𝑒 −𝛽𝛽𝛽𝛽 = 𝐴𝐴 𝑇𝑇 𝑒𝑒 𝑖𝑖𝑖𝑖𝑎𝑎 ,
−𝛽𝛽𝛽𝛽𝑒𝑒 𝛽𝛽𝑎𝑎 + 𝛽𝛽𝛽𝛽′ 𝑒𝑒 −𝛽𝛽𝛽𝛽 = 𝑖𝑖𝑖𝑖𝑖𝑖 𝑇𝑇 𝑒𝑒 𝑖𝑖𝑖𝑖𝑎𝑎 .
• The main aim is to find the expression for the tunnelling probability.
• To acquire this, 𝐴𝐴𝐼𝐼 and 𝐴𝐴 𝑇𝑇 are written in terms of other constant so that
equations at 𝑥𝑥 = 0 give
2𝑖𝑖𝑖𝑖𝐴𝐴𝐼𝐼 = − 𝛽𝛽 − 𝑖𝑖𝑖𝑖 𝐵𝐵 + 𝛽𝛽 + 𝑖𝑖𝑖𝑖 𝐵𝐵′,

• and at 𝑥𝑥 = 𝑎𝑎 give
2𝛽𝛽 (𝛽𝛽+𝑖𝑖𝑖𝑖)
𝐴𝐴 𝑇𝑇 𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖 = 𝐵𝐵𝑒𝑒 −𝛽𝛽𝛽𝛽 and 𝐵𝐵′ = 𝐵𝐵𝑒𝑒 −2𝛽𝛽𝛽𝛽 .
(𝛽𝛽−𝑖𝑖𝑖𝑖) (𝛽𝛽−𝑖𝑖𝑖𝑖)
• The algebra is further ′ simplified by assuming that 𝑒𝑒 −2𝛽𝛽𝛽𝛽 ≪ 1 , which
consequently imply that 𝐵𝐵 ≪ 𝐵𝐵 so that to a good approximation
2𝑖𝑖𝑖𝑖𝐴𝐴𝐼𝐼 ≈ − 𝛽𝛽 − 𝑖𝑖𝑖𝑖 𝐵𝐵.

• Combining two equations results in

𝑖𝑖𝑖𝑖𝑖𝑖 4𝑖𝑖𝑖𝑖𝑖𝑖 −𝛽𝛽𝛽𝛽 .
𝐴𝐴 𝑇𝑇 𝑒𝑒 ≈ 𝐴𝐴
2 𝐼𝐼 𝑒𝑒
(𝛽𝛽−𝑖𝑖𝑖𝑖)
• This implies that the transmission probability is approximated to
16𝑘𝑘 2 𝛽𝛽2 −2𝛽𝛽𝛽𝛽
𝑇𝑇 ≈ 2 2 2 𝑒𝑒 .
𝛽𝛽 +𝑘𝑘
Square-well potential Potential barrier/step
• In the region −∞ ≤ 𝑥𝑥 ≤ 0 • region (−∞ ≤ 𝑥𝑥 ≤ 0)
𝜓𝜓(𝑥𝑥) = 0 𝑑𝑑 2
SE: 2 𝜓𝜓 𝑥𝑥 = −𝑘𝑘 2 𝜓𝜓(𝑥𝑥), with 𝐸𝐸 =
• In the region 0 ≤ 𝑥𝑥 ≤ 𝑎𝑎 𝑑𝑑𝑑𝑑
ℏ2 𝑘𝑘 2
𝑑𝑑 2 2𝑚𝑚
SE:− 2 𝜓𝜓 𝑥𝑥 = −𝑘𝑘02 𝜓𝜓(𝑥𝑥), with 𝐸𝐸 =
ℏ2 𝑘𝑘02
𝑑𝑑𝑑𝑑 Solution:𝜓𝜓 𝑥𝑥 = 𝐴𝐴𝐼𝐼 𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖 + 𝐴𝐴𝑅𝑅 𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖
− 𝑉𝑉0 • 𝐸𝐸 < 𝑉𝑉0 , the region (0 ≤ 𝑥𝑥 ≤ 𝑎𝑎)
2𝑚𝑚
Solution: 𝜓𝜓 𝑥𝑥 = 𝐶𝐶 sin 𝑘𝑘0 𝑥𝑥 𝑑𝑑 2
SE: 2 𝜓𝜓 𝑥𝑥 = 𝛽𝛽2 𝜓𝜓(𝑥𝑥), with 𝐸𝐸 =
• In the region 𝑎𝑎 ≥ 𝑥𝑥 ≥ +∞ 𝑑𝑑𝑑𝑑
ℏ2 𝛽𝛽 2
𝑑𝑑 2 − + 𝑉𝑉0
2𝑚𝑚
SE: 2 𝜓𝜓 𝑥𝑥 = 𝛼𝛼 2 𝜓𝜓(𝑥𝑥), with 𝐸𝐸 =
𝑑𝑑𝑑𝑑
𝛼𝛼2 ℏ2 Solution: 𝜓𝜓 𝑥𝑥 = 𝐵𝐵𝑒𝑒 −𝛽𝛽𝛽𝛽 + 𝐵𝐵𝐵𝑒𝑒 𝛽𝛽𝛽𝛽
− • region (𝑎𝑎 ≥ 𝑥𝑥 ≥ +∞)
2𝑚𝑚
Solution:𝜓𝜓 𝑥𝑥 = 𝐴𝐴𝑒𝑒 −𝛼𝛼𝛼𝛼 SE:
Solution: 𝜓𝜓 𝑥𝑥 = 𝐴𝐴 𝑇𝑇 𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖