Chapter 5: Quantum Mechanics — Detailed Notes

Sections 5.1 through 5.8

Why Quantum Mechanics? (Motivation)

The Bohr model of the atom, while revolutionary, had critical failures:
Only works for hydrogen and one-electron ions (He⁺, Li²⁺)
Cannot explain why some spectral lines are more intense than others
Cannot explain fine structure (spectral lines splitting into multiple lines)
Does not explain how atoms bond to form molecules or solids

A deeper, more general theory was needed. This was developed in 1925–1926 by
Schrödinger, Heisenberg, Born, Dirac, and others — called Quantum Mechanics.
"The discovery of quantum mechanics was nearly a total surprise. It described the
physical world in a way that was fundamentally new. It seemed to many of us a miracle."
— Eugene Wigner

5.1 Quantum Mechanics

Classical vs. Quantum Mechanics
Feature Classical Mechanics Quantum Mechanics

Describes Exact position & momentum Probabilities

Initial state Fully determinable Limited by uncertainty principle

Predicts Exact future trajectory Probability distributions

Valid for Macroscopic objects Atomic & subatomic scale

Key idea: Classical mechanics is just an approximation of quantum mechanics. In the

everyday world, objects contain so many atoms that statistical deviations are invisible — so
classical mechanics "works."

The Wave Function Ψ

The central object in quantum mechanics is the wave function Ψ(x, y, z, t).
Ψ itself has no direct physical meaning
 |Ψ|² = Ψ*Ψ is the probability density — the probability per unit volume of finding
the particle at a given location and time
All measurable information (momentum, energy, position) can be extracted from Ψ
Since Ψ is generally complex (has real and imaginary parts), we write:

Ψ = A + iB

Its complex conjugate is:

Ψ∗ = A − iB

So:

∣Ψ∣2 = Ψ∗ Ψ = A2 + B 2 ≥ 0 (always real and non-negative ✓)

Normalization
Since |Ψ|² is the probability density, the total probability of finding the particle somewhere
must equal 1:

+∞
∫ ​ ∣Ψ∣2 dV = 1 ​

−∞

This is called the normalization condition. Any wave function can be normalized by
multiplying by an appropriate constant.

Requirements for Well-Behaved Wave Functions

For Ψ to represent a real physical particle, it must be:
1. Continuous and single-valued everywhere
2. Its partial derivatives (∂Ψ/∂x, ∂Ψ/∂y, ∂Ψ/∂z) must be continuous, finite, and single-
valued
3. Normalizable — Ψ → 0 as x, y, z → ±∞ so that ∫|Ψ|²dV is finite

Why single-valued? Because probability has only one value at any point in space.

Probability of Finding Particle in a Region

For a 1D particle, the probability of finding it between x₁ and x₂:

x2
Px 1 → x 2 = ∫
​

​ ​
​ ​ ∣Ψ∣2 dx
x1 ​
5.2 The Wave Equation
Classical Wave Equation Review
Before tackling Schrödinger's equation, it helps to review the classical wave equation:

∂2y 1 ∂2y
=
∂x2 v 2 ∂t2
​ ​

where:
y = wave variable (displacement, pressure, electric field, etc.)
v = speed of wave propagation

This governs waves on strings, sound waves, light, etc.

General Solutions
The general solution has the form:

x
y = F (t ± ​)
v

F(t − x/v) → wave traveling in +x direction

F(t + x/v) → wave traveling in −x direction

For a free, undamped, monochromatic harmonic wave:

y = Aeiω(t−x/v)

Using ω = 2πν and v = νλ, this becomes:

y = Aei(ωt−kx)

where k = 2π/λ is the wave number.

Verification (Example 5.1 in text)

Show that y = Ae^{iω(t − x/v)} satisfies the wave equation.
Compute ∂²y/∂x²:

∂y iω ∂2y ω2
=− ⋅y ⇒ =− 2y
∂x ∂x2
​ ​ ​ ​

v v
Compute ∂²y/∂t²:

∂y ∂2y
= iω ⋅ y ⇒ = −ω 2 y
∂t ∂t 2
​ ​

Substituting into the wave equation:

ω2 1
− 2 y = 2 (−ω 2 y) ✓
​ ​

v v

5.3 Schrödinger's Equation: Time-Dependent Form

Free Particle Wave Function
For a quantum particle, the wave function analogous to the classical harmonic wave is:

Ψ = Aei(ωt−kx)

Substituting de Broglie relations: E = hν = ħω and p = h/λ = ħk:

Ψ = Ae(i/ℏ)(Et−px) ​

This is the wave function of a free particle (no forces) with energy E and momentum p
moving in the +x direction.

Deriving Schrödinger's Equation

Step 1: Differentiate Ψ twice with respect to x:

∂Ψ −ip ∂2Ψ p2
= Ψ ⇒ = − 2Ψ
∂x ℏ ∂x2 ℏ
​ ​ ​ ​

So:

∂2Ψ
p2 Ψ = −ℏ2 (1)
∂x2
​

Step 2: Differentiate Ψ once with respect to t:

∂Ψ iE ∂Ψ iE
= Ψ ⋅ (−1) ⇒ =− Ψ
∂t ℏ ∂t ℏ
​ ​ ​ ​

So:
 ∂Ψ
EΨ = iℏ (2)
∂t
​

Step 3: Use the total energy relation (non-relativistic):

p2
E= + U (x, t)
2m
​

Multiply both sides by Ψ:

p2
EΨ = Ψ + UΨ
2m
​

Step 4: Substitute equations (1) and (2):

∂Ψ ℏ2 ∂ 2 Ψ
iℏ =− + UΨ
∂t 2m ∂x2
​ ​ ​

This is the time-dependent Schrödinger equation in 1D:

∂Ψ ℏ2 ∂ 2 Ψ
iℏ =− + UΨ
∂t 2m ∂x2
​ ​ ​ ​

In Three Dimensions

∂Ψ ℏ2 ∂ 2 Ψ ∂ 2 Ψ ∂ 2 Ψ
iℏ =− ( + + ) + UΨ
∂t 2m ∂x2 ∂y 2 ∂z 2
​ ​ ​ ​ ​

Important Notes on Schrödinger's Equation

⚠️ Schrödinger's equation cannot be derived from more fundamental principles — it
IS a fundamental postulate of physics. Its validity rests entirely on agreement with
experiment, which has been extraordinary across all tested domains.
Valid for non-relativistic speeds (v << c)
Newton's F = ma can be derived from Schrödinger's equation when quantities are
treated as averages

5.4 Linearity and Superposition

The Linearity Property
Schrödinger's equation is linear in Ψ — it contains only Ψ and its derivatives to the first
power, with no Ψ² or Ψ³ terms.
Consequence: If Ψ₁ and Ψ₂ are both solutions, then any linear combination:

Ψ = a 1 Ψ1 + a 2 Ψ2
​ ​ ​ ​

is also a valid solution (a₁, a₂ are complex constants).

This is the Superposition Principle for quantum waves.

Why This Matters: Double-Slit Experiment

Consider electrons passing through two slits toward a screen:
Slit 1 only open: probability density P₁ = |Ψ₁|²
Slit 2 only open: probability density P₂ = |Ψ₂|²
Both slits open: You might naively expect P = P₁ + P₂, but this is WRONG!

Correct treatment: Wave functions add, not probabilities:

Ψ = Ψ1 + Ψ2 ​ ​

P = ∣Ψ∣2 = ∣Ψ1 + Ψ2 ∣2 = ∣Ψ1 ∣2 + ∣Ψ2 ∣2 + Ψ∗1 Ψ2 + Ψ∗2 Ψ1

​ ​ ​ ​ ​ ​ ​ ​

= P1 + P2 + Ψ∗1 Ψ2 + Ψ∗2 Ψ1
​ ​ ​ ​ ​ ​ ​

interference terms

The last two terms produce the interference pattern (alternating bright and dark fringes)
observed in the experiment — identical to what happens with light!
Key insight: Quantum particles exhibit wave interference. The "path" of a particle is not
determined until measurement.

5.5 Expectation Values

What is an Expectation Value?
In quantum mechanics, we cannot predict the exact result of a single measurement. But we
can predict the average result over many identical measurements. This average is called the
expectation value.
Expectation Value of Position
For N particles distributed along x-axis with Nᵢ particles at position xᵢ:

∑ Ni x i
ˉ=
​ ​

x
∑ Ni
​

For a quantum particle, replace Nᵢ with probability Pᵢ = |Ψᵢ|² dx:

+∞
∫−∞ x∣Ψ∣2 dx
⟨x⟩ =
​

+∞
∣Ψ∣2
​

∫−∞ ​
dx

For a normalized wave function (denominator = 1):

+∞
⟨x⟩ = ∫ ​
x∣Ψ∣2 dx ​

−∞

Expectation Value of Any Function of x

+∞
⟨G(x)⟩ = ∫ ​ G(x)∣Ψ∣2 dx
−∞

Worked Example (from text) — Example 5.2

Problem: A particle has wave function Ψ = ax for 0 ≤ x ≤ 1, and Ψ = 0 elsewhere.
(a) Probability of finding particle between x = 0.45 and x = 0.55:

0.55 0.55 0.55

x3
P =∫ ∣ax∣ dx = a ∫
2 2
x dx = a [ ]2 2
3 0.45
​ ​ ​ ​

0.45 0.45

(0.55)3 − (0.45)3
2
=a ⋅ = 0.0251a2
3
​

(b) Expectation value of position:

1 1
x4 1 a2
⟨x⟩ = ∫ x ⋅ ∣ax∣ dx = a ∫
2 2 3
x dx = a ⋅ 2
=
4 4
​ ​ ​ ​ ​ ​

0 0 0
5.6 Operators
Why Operators?
Expectation values of position and potential energy are straightforward (multiply by |Ψ|²).
But momentum and energy cannot be expressed as simple functions of x, because of the
uncertainty principle.
The solution: represent physical quantities as mathematical operators that act on the wave
function.

Momentum and Energy Operators

Starting from the free-particle wave function Ψ = Ae^{(i/ħ)(Et−px)}, differentiate:

∂Ψ −ip ℏ ∂Ψ
= Ψ ⇒ = pΨ
∂x ℏ i ∂x
​ ​ ​ ​

∂Ψ iE ∂Ψ
= Ψ ⋅ (−1) ⇒ iℏ = EΨ
∂t ℏ ∂t
​ ​ ​

This gives the quantum mechanical operators:

ℏ ∂
p^ =
i ∂x
​ ​ ​ ​

^ = iℏ ∂
E
∂t
​ ​

Table of Operators
Physical Quantity Operator

Position x x

Momentum p (ħ/i)(∂/∂x)

Potential energy U(x) U(x)

Kinetic energy KE −(ħ²/2m)(∂²/∂x²)

Total energy (Hamiltonian) Ĥ −(ħ²/2m)(∂²/∂x²) + U

Total energy Ê iħ(∂/∂t)

Expectation Value Using Operators
For any operator Ĝ:

+∞
⟨G⟩ = ∫ ​
^ Ψ dx
Ψ∗ G ​

−∞

For momentum:

+∞
ℏ ∂
⟨p⟩ = ∫ Ψ∗ ( ) Ψ dx
i ∂x
​ ​ ​

−∞

For energy:

+∞
∂
⟨E⟩ = ∫ Ψ∗ (iℏ ) Ψ dx
∂t
​ ​

−∞

⚠️ Order matters! Always write Ψ* Ĝ Ψ, not Ψ Ĝ Ψ* — operators act on what's to their

right.

The Hamiltonian Operator

Using KE = p²/2m and substituting the momentum operator:

^ ℏ2 ∂ 2
H=− +U
2m ∂x2
​ ​

This is the Hamiltonian operator, and Schrödinger's equation can be written compactly as:

^ Ψ = EΨ
H

5.7 Schrödinger's Equation: Steady-State Form

Separating Time and Space
When potential energy U depends only on position (not time), we can separate Ψ into a
spatial part and a time part:

Ψ(x, t) = ψ(x) ⋅ e−(iE/ℏ)t

The time factor has the same form as a free particle: e^{−(iE/ħ)t}.
Substituting into the time-dependent Schrödinger equation:

−iE ℏ 2 d2 ψ
iℏ ⋅ ( ) ψe−(iE/ℏ)t = [− + U ψ ] e−(iE/ℏ)t
ℏ 2m dx 2
​ ​ ​

Dividing both sides by e^{−(iE/ħ)t}:

d2 ψ 2m
+ 2 (E − U )ψ = 0
dx2 ℏ
​ ​ ​

This is the time-independent (steady-state) Schrödinger equation in 1D.

In Three Dimensions

∂ 2 ψ ∂ 2 ψ ∂ 2 ψ 2m
+ + + 2 (E − U )ψ = 0
∂x2 ∂y 2 ∂z 2 ℏ
​ ​ ​ ​

Eigenvalues and Eigenfunctions

The steady-state equation only has acceptable solutions (normalized, continuous, single-
valued) for certain specific values of energy — called eigenvalues Eₙ.
The corresponding wave functions are called eigenfunctions ψₙ.
This is how energy quantization emerges naturally from quantum mechanics — no
special assumptions needed, unlike the Bohr model!
Examples of eigenvalues:
4
Hydrogen atom: En = − 32πme 1
​

2 ε2 ℏ2 ⋅ ​

n2
​

0
​

Angular momentum: L = l(l + 1) ℏ, where l = 0, 1, 2, ..., (n−1)

​

Eigenvalue Equation
If a quantity G is quantized, its wave functions satisfy:

^ ψ n = Gn ψ n
G ​ ​ ​

where Gₙ is a real number (the measurable value).

Schrödinger's equation in eigenvalue form:

^ ψn = E n ψn
H ​ ​ ​
Worked Example (from text) — Example 5.3
Find the eigenvalue of d²/dx² for the eigenfunction ψ = e^{2x}.

^ d2 2x d
Gψ = 2 (e ) =
​ (2e2x ) = 4e2x = 4ψ
​

dx dx

So the eigenvalue is G = 4. ✓

Analogy: Standing Waves on a String

The energy quantization in quantum mechanics is directly analogous to the allowed
wavelengths of standing waves on a string of length L fixed at both ends:

2L
λn = , n = 0, 1, 2, 3, …
n+1
​ ​

Only certain discrete wavelengths are allowed — just as only certain discrete energies are
allowed in quantum systems.

5.8 Particle in a Box (Infinite Square Well)

Setup
A particle of mass m is trapped between x = 0 and x = L by infinitely hard walls:
U = 0 for 0 < x < L (inside box)
U = ∞ for x ≤ 0 and x ≥ L (outside box)

Since the particle cannot have infinite energy, it cannot exist outside, so:

ψ=0 for x ≤ 0 and x ≥ L

Solving Schrödinger's Equation Inside the Box

With U = 0, the steady-state equation becomes:

d2 ψ 2mE
+ 2 ψ=0
dx2 ℏ
​ ​

Let k 2 = 2mE
ℏ2
. This is a standard second-order ODE with solution:
​

ψ = A sin(kx) + B cos(kx)
Applying Boundary Conditions
At x = 0: ψ(0) = 0

A sin(0) + B cos(0) = B = 0 ⇒ B=0

At x = L: ψ(L) = 0

A sin(kL) = 0

Since A ≠ 0 (otherwise no particle), we need:

kL = nπ, n = 1, 2, 3, …

nπ
⇒ kn =
​ ​

Energy Eigenvalues
Substituting back:

2mEn n2 π 2
kn2 = =
​

ℏ2 L2
​ ​ ​

n2 π 2 ℏ 2 n 2 h2
En = = , n = 1, 2, 3, …
2mL2 8mL2
​ ​ ​ ​

Key features:
Energy is quantized — only discrete values are allowed
n is the quantum number (n = 0 is excluded because ψ = 0 everywhere → no particle)
Energy scales as n² and as 1/L² (smaller box = higher energy)
Ground state (n=1) has minimum energy E₁ = h²/(8mL²) ≠ 0 (zero-point energy!)

Wave Functions (Eigenfunctions)

nπx
ψn = A sin( ​ ) ​

Normalization
To find A, apply the normalization condition:
 L
∫ ​ ∣ψn ∣2 dx = 1
​

L
nπx
A ∫ 2
​ sin2 ( ) dx = 1
​

0 L

Using the identity sin2 θ = 12 (1 − cos 2θ):

​

L 2
A2 ⋅ =1 ⇒ A=
2
​ ​ ​

Final Normalized Wave Functions

2 nπx
ψn =
​ sin(
​ ​ ), ​ n = 1, 2, 3, … ​

L L

Physical Interpretation
ψₙ has n antinodes (bumps) inside the box
|ψₙ|² is the probability density
For n = 1 (ground state): max probability at center (x = L/2)
For n = 2: zero probability at center! (a node exists there)
Higher n → more oscillations → higher energy

Expectation Value of Position (Example 5.5)

L
2 L nπx
⟨x⟩ = ∫ ​
x∣ψn ∣ dx = ∫ x sin2 (
​
2
) dx ​ ​ ​

0 L 0 L

Using the integral identity and evaluating:

L
⟨x⟩ = for all n
2
​ ​

Interpretation: On average, the particle is always at the center — regardless of quantum

number. This reflects the symmetry of the well.

Probability in a Region (Example 5.4)

Problem: Find probability of finding particle between x = 0.45L and x = 0.55L for n = 1 and
n = 2.
 0.55L
2 0.55L 2 nπx
P =∫ ​ ∣ψn ∣ dx = ∫
​ sin (
2
) dx ​ ​ ​

0.45L L 0.45L L

For n = 1:

0.55L
1 2nπx
P =[ − sin( )]
x
L 2nπ
​ ​ ​ ​

L 0.45L

Pn=1 ≈ 0.198 = 19.8%

​

This is twice the classical prediction of 10%! The particle prefers the center in its ground
state.
For n = 2:

Pn=2 ≈ 0.0065 = 0.65% ​

This is very small because ψ₂ has a node at x = L/2, so the particle almost never appears
there!

Expectation Value of Momentum

L
ℏ dψn
⟨p⟩ = ∫ ψn∗ ⋅ dx = 0
​

​ ​ ​ ​

0 i dx

Why? The particle bounces back and forth — equal time moving left and right — so average
momentum is zero. But the magnitude of momentum is:

nπℏ p2n
∣pn ∣ = ℏkn = ⇒ En = ✓
​

2m
​ ​ ​ ​ ​

Correspondence Principle Check

As n → ∞, the probability density |ψₙ|² oscillates so rapidly that it averages to 1/L (uniform
distribution) — identical to the classical result of equal probability everywhere in the box.
✓
Summary Table: Key Results for Sections 5.1–5.8
Topic Key Result

Wave function

Normalization ∫

Superposition Ψ = a₁Ψ₁ + a₂Ψ₂ (wave functions add, not probabilities)

Expectation value ⟨x⟩ = ∫x

Momentum operator p̂ = (ħ/i)(∂/∂x)

Energy operator Ê = iħ(∂/∂t)

Time-dep. Schrödinger eq. iħ∂Ψ/∂t = −(ħ²/2m)∇²Ψ + UΨ

Steady-state Schrödinger eq. ψ'' + (2m/ħ²)(E−U)ψ = 0

Particle in box: energies Eₙ = n²h²/(8mL²)

Particle in box: wave functions ψₙ = √(2/L) sin(nπx/L)

Average position in box ⟨x⟩ = L/2 for all n

Relevant Numerical Exercises (for Topics 5.1–5.8)

The following exercises from Chapter 5 are directly relevant to the topics covered above:

Section 5.1 (Wave Functions, Normalization)

Exercise 1 & 2 — Identify which wave functions are physically acceptable
Exercise 3 — Determine which functions can be Schrödinger solutions
Exercise 4 — Find normalization constant A for ψ = Axe^{−x²/2}
Exercise 5 — Find A for ψ = A cos²x; find probability in region

Section 5.2 (Wave Equation)

Exercise 6 — Verify y = A cos(ωt − x/v) satisfies wave equation
Exercise 7 — Analyze the free particle wave function ψ = Ae^{(i/ħ)(Et−px)}

Section 5.4 (Linearity & Superposition)

Exercise 8 — Prove Schrödinger's equation is linear
Section 5.6 (Operators)
Exercise 9 — Show p̂ x̂ and x̂ p̂ don't commute (related to uncertainty principle)
Exercise 10 — Find eigenvalues of d²/dx² for eigenfunction sin(nπx)

Section 5.7 (Steady-State Form)

Exercise 11 — Derive steady-state Schrödinger equation from the wave equation

Section 5.8 (Particle in a Box)

Exercise 12 — Verify correspondence principle as n → ∞
Exercise 13 — Explain behavior of ψ in a variable potential well (Fig. 5.17)
Exercise 14 — Particle in box from x₀ to x₀ + L (shifted box)
Exercise 15 — Prove orthogonality of eigenfunctions
Exercise 16 — Box divided into three sections; total energy as function of divider
position
Exercise 17 — Find expectation value ⟨x²⟩ for particle in box
Exercise 18 — Normalize the combination ψ = B[sin(πx/L) + sin(2πx/L)]
Exercise 19 — Probability of particle in box between x = 0 and x = L/n in state n
Exercise 20 — Standard deviation of position; uncertainty in ⟨x⟩
Exercise 21 — 3D cubic box: find normalization constant A
Exercise 22 — Ground state probability in 3D box: regions 0 to L/4 and 0 to L/2
Exercise 23 — Find allowed energies for 3D cubic box; compare with 1D

Note: Exercises 24–38 cover sections 5.9–5.11 and the appendix (Tunnel Effect,
Harmonic Oscillator) which are beyond our current scope (5.1–5.8).

Notes compiled from: Beiser, "Concepts of Modern Physics," Chapter 5