QUANTUM

MECHANICS
PHY 361
 I don’t like quantum
2

mechanics, and I’m

sorry I ever had
anything to do with it”
-Erwin Schrödinger-
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QUANTUM MECHANICS
(PHY 361)

INSTRUCTOR: ISAAC KWESI ACQUAH

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PARTICLE IN 1-D BOX

LECTURE 8
 Introduction 5
❑ The particle in a box problem is a common application of a quantum mechanical model to a
simplified system consisting of a particle moving horizontally within an infinitely deep well
from which it cannot escape.

❑ A particle in a 1-dimensional box is a fundamental quantum mechanical approximation

describing the translational motion of a single particle confined inside an infinitely deep well
from which it cannot escape.

❑ The solutions to the problem give possible values of 𝐸 and ψ that the particle can possess. 𝐸
represents allowed energy values and ψ(𝑥) is a wavefunction, which when squared gives the
probability of locating the particle at a certain position within the box at a given energy level.

❑ To solve the problem for a particle in a 1-dimensional box, we must define the potential energy,
V, solve Schrodinger’s equation, solve for the wavefunctions, and solve for the allowed energies.
 Potential Energy V 6

❑ The potential energy is 0 inside the box (V=0 for 0<x<L) and goes to infinity at the walls of
the box (V=∞ for x<0 or x>L)

❑ We assume the walls have infinite potential energy to ensure that the particle has
zero probability of being at the walls or outside the box.

❑ Doing so significantly simplifies our later mathematical calculations as we employ

these boundary conditions when solving the Schrödinger Equation.
 Solve the Schrödinger Equation 7

❑ The time-independent Schrodinger’s equation for a particle of mass, 𝑚 moving in

one direction with energy 𝐸 is
−ħ2 𝑑2 Ѱ(𝑥)
2
+ 𝑉 𝑥 Ѱ(𝑥) = 𝐸Ѱ(𝑥)
2𝑚 𝑑𝑥

❑ This equation can be modified for a particle of mass 𝑚 free to move parallel to the x-
axis with zero potential energy (𝑉 = 0 𝑒𝑣𝑒𝑟𝑦𝑤ℎ𝑒𝑟𝑒) resulting in the quantum
mechanical description of free motion in one dimension:
−ħ2 𝑑2 Ѱ(𝑥)
2
= 𝐸Ѱ(𝑥)
2𝑚 𝑑𝑥
❑ This equation gives the general solution of:
Ѱ 𝑥 = 𝐴 sin(𝑘𝑥) + 𝐵 cos(𝑘𝑥)

Where A, B, and k are

 The Wavefunction
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❑ The solution to the Schrödinger equation we found above is the general solution for
a 1-dimensional system.

❑ We now need to apply our boundary conditions to find the solution to our
particular system.
❑ According to our boundary conditions, the probability of finding the particle at 𝑥 =
0 𝑜𝑟 𝑥 = 𝐿 is zero.
❑ When 𝑥 = 0, then sin 0 = 0 and cos 0 = 1; therefore 𝐵 must equal 0 to fulfill this
boundary condition:
Ѱ 𝑥 = 𝐴 sin(𝑘𝑥)
❑ We can now solve for our constants (A and k) systematically to define the wavefunction
 Solving for k
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Differentiate the wavefunction with respect to 𝑥:
Ѱ 𝑥 = 𝐴 sin(𝑘𝑥)
𝑑 𝑑
Ѱ 𝑥 = 𝐴 sin(𝑘𝑥)
𝑑𝑥 𝑑𝑥
𝑑
Ѱ 𝑥 = 𝑘𝐴 cos 𝑘𝑥 ………………………………………………………….. (1)
𝑑𝑥
Differentiate again with respect to 𝑥:

𝑑2 𝑑 𝑘𝐴 cos 𝑘𝑥
2
Ѱ 𝑥 =
𝑑𝑥 𝑑𝑥
𝑑2 2 𝐴 sin 𝑘𝑥
Ѱ 𝑥 = −𝑘
𝑑𝑥 2
Since Ѱ 𝑥 = 𝐴 sin(𝑘𝑥) , then
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𝑑2 2 Ѱ 𝑥
Ѱ 𝑥 = − 𝑘 ……………………………………………………………….. (2)
𝑑𝑥 2
Re-arranging the Schrodinger’s equation at zero potential;
−ħ2 𝑑2 Ѱ(𝑥)
2
= 𝐸Ѱ(𝑥)
2𝑚 𝑑𝑥

𝑑2 Ѱ(𝑥) 2𝑚𝐸 NB: ħ =

ℎ

2
= − 2 Ѱ(𝑥) 2𝜋
𝑑𝑥 ℎ
𝑑2 Ѱ(𝑥) 8𝜋 2 𝑚𝐸
2
=− 2
Ѱ(𝑥) ……………………………………………………………… (3)
𝑑𝑥 ℎ 𝟏
Comparing equation eqn (2) and eqn (3) 𝟖𝝅𝟐 𝒎𝑬 𝟐
𝒌=
ℎ𝟐
This is the simplest way of finding k
Now we plug k into our wavefunction, Ѱ 𝑥 = 𝐴 sin(𝑘𝑥) 11

Ѱ 𝑥 = 𝐴 sin(𝑘𝑥)

1
8𝜋 2 𝑚𝐸 2
Ѱ 𝑥 = 𝐴 sin 𝑥
ℎ2

Solving for A
❑ To determine A, we have to apply the boundary conditions again.

❑ Recall that at the boundary conditions, the probability of finding the particle at 𝑥 =
0 𝑜𝑟 𝑥 = 𝐿 is zero.
When 𝑥 = 𝐿; Ѱ 𝑥 = 0
1 12
8𝜋 2 𝑚𝐸 2
Ѱ 𝑥 = 𝐴 sin 𝑥
ℎ2

  = 0
1
8𝜋 2 𝑚𝐸 2
𝐴 sin 𝐿 =0
ℎ2 0
0 L
x

Applying the concept of sine functions; this is only true when

1
1
8𝜋 2 𝑚𝐸 2
⟹ 8𝜋 2 𝑚𝐸 2 𝑛𝜋
𝐿 = 𝑛𝜋 = Where 𝑛 = 1,2,3,4, … … . .
ℎ2 ℎ2 𝐿
Plugging this back in gives us:
𝑛𝜋
Ѱ 𝑥 = 𝐴 sin 𝑥
𝐿
❑ To determine AA, recall that the total probability of finding the particle inside the
box is 1, meaning there is no probability of it being outside the box 13

❑ When we find the probability and set it equal to 1, we are normalizing the wave
function. 𝐿
න Ѱ 𝑥 2 𝑑𝑥 = 1
0
𝐿
𝑛𝜋 𝑛𝜋
න 𝐴 sin 𝑥 𝐴 sin 𝑥 𝑑𝑥 = 1
0 𝐿 𝐿
𝐿
2 2
𝑛𝜋
𝐴 න sin 𝑥 𝑑𝑥 = 1
0 𝐿
1
Using the trig identity; sin2 𝑥 = 1 − cos 2𝑥
2

𝐿
2
1 𝑛𝜋
𝐴 න 1 − cos 2 𝑥 𝑑𝑥 = 1
0 2 𝐿
 1 2 𝐿 𝑛𝜋
𝐴 න 1 − cos 2 𝑥 𝑑𝑥 = 1 14
2 0 𝐿
1 2 𝐿 𝐿
𝑛𝜋
𝐴 න 𝑑𝑥 − න cos 2 𝑥 𝑑𝑥 = 1
2 0 0 𝐿
1 2
𝐴 𝐿 =1
2
2
𝐴=
𝐿

❑ Which results in the normalized wavefunctions for a particle in a 1-dimensional box:

2 𝑛𝜋
Ѱ 𝑥 = sin 𝑥
𝐿 𝐿
 The Allowed Energies
15

Consider the normalized wavefunction,

2 𝑛𝜋 and the reduced Schrodinger’s equation

Ѱ 𝑥 = sin 𝑥 where the potential energy is zero,
𝐿 𝐿

−ħ2 𝑑 2 Ѱ(𝑥)
2
= 𝐸Ѱ(𝑥)
2𝑚 𝑑𝑥
The allowed energies for a particle in a box:
1 𝑛𝜋
8𝜋 2 𝑚𝐸 2 But, 𝑘 =
𝑘= 𝐿
ℎ2
𝑛𝜋 2 8𝜋 2 𝑚𝐸 ⟹
𝑛2 𝜋 2 8𝜋 2 𝑚𝐸
= 2
=
𝐿 ℎ2 𝐿 ℎ2
𝒏𝟐 𝒉𝟐
𝑬=
𝟖𝒎𝑳𝟐
 𝒏𝟐 𝒉𝟐
❑ Equation 𝑬 = is a very important result and tells us that:
𝟖𝒎𝑳𝟐
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❑ The energy of a particle is quantized.

❑ The lowest possible energy of a particle is NOT zero. This is called the zero-point
energy and means the particle can never be at rest because it always has some
kinetic energy.

❑ This is also consistent with the Heisenberg Uncertainty Principle: if the particle had
zero energy, we would know where it was in both space and time.
 The Implications of the wavefunction of a particle in a Box
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❑ The wavefunction for a particle in a box at the n=1 and n=2 energy levels look like this fig A:

❑ The probability of finding a particle a certain spot in the

box is determined by squaring ψ. A

❑ The probability distribution for a particle in a box at

the n=1 and n=2 energy levels looks like this fig B:

❑ Notice that the number of nodes (places where the

particle has zero probability of being located)
increases with increasing energy n.
❑ Also note that as the energy of the particle B
becomes greater, the quantum mechanical
model breaks down as the energy levels get
closer together and overlap, forming a
continuum.
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END OF LECTURE