The wave functions and probability densities

for a Particle in a Rigid Box

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  The Particle in a Rigid Box
a graphical representation of the particle-in-a-
box problem, shows the potential energy of the
particle–environment system as a function of
the position of the particle.
As long as the particle is inside the box, the
potential energy of the system does not depend
on the location of the particle and we can
choose its constant value to be zero. Outside
the box, we must ensure that the wave function
is zero. We can do so by defining the system’s
potential energy as infinitely large if the particle
were outside the box. Therefore, the only way a
particle could be outside the box is if the system
has an infinite amount of energy, which is
impossible.

Consider a particle that is confined to some finite interval on the x axis, and moves freely inside
that interval. This is a one-dimensional rigid box, and is often called the infinite square well.
An example would be an electron inside a length of very thin conducting wire. The electron
would move freely back and forth inside the wire, but could not escape from it.

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  The Particle in a Rigid Box
(the infinite square well)

a)The central tube is grounded, so a test charge inside this tube has zero electric potential
energy and experiences no electric force.
b)A charge whose total energy is less than 𝑞𝑉 is confined ‫ محصورة‬to the central cylinder by the
strong repulsive forces in the gaps at 𝑥 = 0 and 𝑥 = 𝐿.
c) As V is increased and the gaps between cylinders are narrowed, the potential energy
approaches that of the infinite square well.

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 The Particle in a Rigid Box

As long as the particle is inside the box, the

potential energy of the system does not depend
on the location of the particle and we can choose
its constant value to be zero. Outside the box, we
must ensure that the wave function is zero. We
can do so by defining the system’s potential
energy as infinitely large if the particle were
outside the box.

Consider a quantum particle of mass m moving in a one dimension rigid box of length 𝑎, with no forces
acting on it inside the box between 𝑥 = 0 and 𝑥 = 𝐿. So the potential 𝑈 = 0 inside the box.
Therefore, the particle’s total energy is just its kinetic energy. In quantum mechanics, we write the
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kinetic energy as 𝒑𝟐 /𝟐𝒎, rather than 𝑚𝑢2 , because of the de Broglie relation, 𝜆 = ℎ/𝑝. (This will
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make more sense later.) So we write the total energy as
1 𝒑 𝟐
𝐸 = 𝐾. 𝐸 = 𝑚𝑢2 =
2 𝟐𝒎

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  The Particle in a Rigid Box
We found that the position dependent part of the wave function for a standing
wave is given by:
𝜓(𝑥) = 𝐴 sin(𝑘𝑥)

If we assume that ψ(x) is continuous, then it must also vanish at 𝑥 = 0 𝑎𝑛𝑑 𝑥 = 𝐿:

𝝍(𝟎) = 𝝍(𝑳) = 𝟎

The boundary condition 𝜓(𝐿) = 0 requires that, 𝝍 𝑳 = 𝑨𝒔𝒊𝒏 𝒌𝑳 = 𝟎 which implies that,

𝑘𝐿 = 𝜋, 𝑜𝑟 2𝜋, 𝑜𝑟 3𝜋, … 𝑂𝑟 𝒌 = 𝒏𝝅/𝑳 𝑛 = 1, 2, 3, …

𝟐𝝅 𝟐𝑳
= 𝒏𝝅/𝑳 𝝀= 𝒏 = 𝟏, 𝟐, , 𝟑, . .
In terms of the wavelength, this condition implies that 𝝀 𝒏

where n = 1, 2, 3, . . . . Therefore, only certain wavelengths for the particle are allowed! Each of the allowed
wavelengths corresponds to a quantum state for the system, and n is the quantum number.
𝒏𝝅
𝝍(𝒙) = 𝑨 𝒔𝒊𝒏( 𝒙)
𝑳

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  The Particle in a Rigid Box
∴ The allowed wave functions for a particle in a box:
𝒏𝝅
𝜳𝒏 𝒙 = 𝑨 𝒔𝒊𝒏( 𝒙)
𝑳
The wave functions 𝛹𝑛 for a particle in a box with n = 1, 2, and 3 in shown in the figure

To obtain these values of the momentum and energy as following:

The important point is that quantization of the wavelength λ implies quantization of
the momentum, and hence also of the energy.
𝒉 𝒏𝒉 𝒑𝟐 𝟐𝑳
𝒑 = 𝒉/𝝀 = = Plugging this into 𝑬= 𝝀=
𝟐𝑳/𝒏 𝟐𝑳 𝟐𝒎 𝒏

Therefore, the energy of the system is simply the kinetic energy of the particle and the allowed values are given by

𝒉𝟐 This expression shows that the energy of the

𝑬𝒏 = 𝟐
𝒏𝟐 𝒏 = 𝟏, 𝟐, 𝟑, …
𝟖𝒎𝑳 particle is quantized.

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 𝒉
 The Particle in a Rigid Box ℏ=
𝟐𝝅
We have chosen the potential energy of the system to be zero when the particle is inside the box. Therefore,
the energy of the system is simply the kinetic energy of the particle and the allowed values are given by

𝟏 𝒑 𝟐 𝒏𝒉 𝟐𝑳 𝟐
𝟐
𝑬𝒏 = 𝒎𝒖 = =
𝟐 𝟐𝒎 𝟐𝒎

𝒉𝟐 𝟐 ℏ𝟐 𝝅𝟐 𝟐
𝑬𝒏 = 𝒏 𝑬𝒏 = 𝒏
𝟖𝒎𝑳𝟐 𝟐𝒎𝑳𝟐

This expression shows that the energy of the particle is quantized.

The ground state energy which is the lowest energy state for any system.
For the particle in a box, the ground state corresponds to 𝑛 = 1

𝒉𝟐
𝑬𝟏 = 𝑬𝒏 = 𝒏𝟐 𝑬𝟏
𝟖𝒎𝑳𝟐

Because 𝑬𝒏 = 𝒏𝟐 𝑬𝟏 , the excited states corresponding to 𝑛 = 2, 3, 4, . . . have energies given by

𝟒𝑬𝟏, 𝟗𝑬𝟏, 𝟏𝟔𝑬𝟏, . . . .

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The energy of the particle is quantized

𝒉𝟐
𝑬𝒏 = 𝟐
𝒏𝟐
𝟖𝒎𝑳

The Figure is an energy-level diagram describing the energy values

of the allowed states. Because the lowest energy of the particle in
a box is not zero, then, according to quantum mechanics, the
particle can never be at rest! The smallest energy it can have,
corresponding to 𝑛 = 1, is called the ground-state energy. This
result contradicts the classical viewpoint, in which 𝐸 = 0 is an
acceptable state, as are all positive values of E.

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 The wave functions and probability densities for a Particle in a Rigid Box
Returning to the wavefunctions
Stationary states for a 𝒏𝝅𝒙
𝟁𝒏 𝒙 = 𝑨 𝐬𝐢𝐧 𝑓𝑜𝑟 0 < 𝑥 < 𝐿 𝑎𝑛𝑑 𝑛 = 1, 2, . . .
particle in a box 𝑳

For each value of the quantum number n there is a specific wavefunction 𝟁𝒏 𝒙 describing the state of
the particle with energy 𝑬𝒏 .

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 ∞
𝟐𝑳
𝝀= |𝝍(𝒙))|𝟐 = 𝟏
 The wave functions and probability densities for a 𝒏 −∞
Particle in a Rigid Box

Wave functions 𝟐𝝅𝒙 𝒏𝝅𝒙

𝟁𝒏 𝒙 = 𝑨 𝐬𝐢𝐧 = 𝑨 𝐬𝐢𝐧
for a particle in a 𝟐𝑳/𝒏 𝑳
box

Normalizing this wave function shows that 𝑨= 𝟐/𝑳 solve it?

Therefore, the normalized wave function for the particle in a

box is
𝟐 𝒏𝝅𝒙
𝟁𝒏 𝒙 = 𝒔𝒊𝒏
𝑳 𝑳

a general wave function 𝟁 can have positive and negative values, |c|2 is always positive.
Because 𝟁 2 represents a probability density, a negative value for 𝟁 2 would be
meaningless.
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 𝒏𝝅𝒙
To evaluate the constant A 𝟁𝒏 𝒙 = 𝑨 𝐬𝐢𝐧
𝑳

To complete our solution, we need to evaluate the constant A in the wave function.
In order to do this, we impose the condition that the wave function has to be
normalized, i.e., the probability of finding the particle anywhere in space is 1.
∞
|𝟁𝒏 𝒙 |𝟐 𝒅𝒙 = 1
−∞
𝑳
𝟁 𝒙 𝒏 = 0 outside of the box, then the relation above can be |𝝍(𝒙))|𝟐 = 1
rewritten as 𝑳 𝟎
Substituting for𝟁𝒏 𝒙 yields 𝟐 𝟐
𝑨 |𝟁𝒏 𝒙 | 𝒅𝒙 = 1
𝟎
𝑳
𝟐 𝟐
𝒏𝝅𝒙
𝑨 𝒔𝒊𝒏 𝒅𝒙 = 𝟏
𝟎 𝑳
𝟐
𝑳
𝑨 =𝟏 ∴𝑨= 𝟐/𝑳
𝟐
𝟐 𝒏𝝅𝒙
A is called the normalization constant. Thus, the complete wave 𝟁𝒏 𝒙 = 𝒔𝒊𝒏
𝑳 𝑳
function is
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 Example 5 : Microscopic and Macroscopic Particles in 1eV = 1.602 × 10−19 𝐽
Boxes

(A) An electron is confined between two impenetrable walls 0.200 nm apart. Determine the
energy levels for the states n = 1, 2, and 3.
Solution: imagine that the particle is an electron and the walls are very close together
𝒉𝟐 𝟐
the quantization energy equation 𝑬𝒏 = 𝟖𝒎𝑳𝟐 𝒏

Use for the n = 1 state

Use 𝑬𝒏 = 𝒏𝟐 𝑬𝟏

for the n = 1and n=3 states

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(B) An electron is confined between two impenetrable walls 0.200 nm apart.
Find the speed of the electron in the n = 1 state
Solution: Recognize that the kinetic energy of the particle is equal to the system
energy and substitute 𝐸𝑛 for K:

1 2𝐸𝑛
𝐸𝑛 = 𝐾. 𝐸 = 𝑚𝑒 𝑢2 𝑢=
2 𝑚𝑒

Simply placing the electron in the box results in a minimum speed of the electron equal to
0.6% of the speed of light!

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(C) A 0.500-kg baseball is confined between two rigid walls of a stadium that can be modeled as a box
of length 100 m. Calculate the minimum speed of the baseball.
Solution:
imagine that the particle is a baseball and the walls are those of the stadium.
𝒉𝟐
𝑬𝒏 = 𝒏𝟐
𝟖𝒎𝑳𝟐

for the n = 1 state:

The speed: 2𝐸𝑛

𝑢=
𝑚𝑒

This speed is so small that the object can be considered to be at rest, which is what one would expect for the
minimum speed of a macroscopic object.

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 EXAMPLE 3The Expectation Values for the Particle in a Box
A particle of mass m is confined to a one-dimensional box between 𝑥 = 0 and 𝑥 = 𝐿. Find the expectation value
of the position 𝒙 of the particle in the state characterized by quantum number n.
Solution

This result shows that the expectation value of x is at the center of the box for all values of n, which you would
expect from the symmetry of the square of the wave functions (the probability density) about the center as in
figure.

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𝑇ℎ𝑒 𝑛 = 2 wave function in Figure has a value of zero at the midpoint of the box. Can the expectation
value of the particle be at a position at which the particle has zero probability of existing? Remember that
the expectation value is the average position. Therefore, the particle is as likely to be found to the right of
the midpoint as to the left, so its average position is at the midpoint even though its probability of being
there is zero.

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The end, thank you

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