IISER BHOPAL · QUANTUM PHYSICS 2026 · POST MID-SEM

ASSIGNMENT II

Particle in a Box — Complete Solutions

Problems 1–6 · Detailed Step-by-Step Workings

PROBLEM 1 Probability Distributions for Ψ 3 , Ψ 4 , Ψ 5

Consider a particle in a box. Plot the probability distribution for

Ψ 3 (x, t), Ψ 4 (x, t), and Ψ 5 (x, t).

THE PARTICLE-IN-A-BOX EIGENSTATES

We consider an in!nite square well of length L with V = 0 for

0 < x < L and V = ∞ outside. The time-independent Schrödinger
equation inside is:

ℏ 2 d2 ψ
− = E ψ, ψ(0) = ψ(L) = 0
2m dx 2

The normalised energy eigenstates (stationary states) are:

 ψ n (x) = √
2
),
nπx
sin( n = 1, 2, 3, …
L L

n2 π2 ℏ 2
with energy eigenvalues E n = . The full time-dependent
2mL 2
wavefunctions are:

Ψ n (x, t) = ψ n (x) e −iEn t/ℏ

PROBABILITY DENSITY

2
The probability density is |Ψ n (x, t)| 2 . Since e −iEn t/ℏ = 1, the
time dependence drops out:

KEY RESULT

2
sin 2 ( )
nπx
|Ψ n (x, t)| 2 = |ψ n (x)| 2 =
L L

This is time-independent — stationary states have static probability

densities. The state |Ψ n | 2 has n peaks (antinodes) of equal height 2/L
and n − 1 interior nodes where the probability is zero.

PLOTS OF |Ψ 3 | 2 , |Ψ 4 | 2 , |Ψ 5 | 2

|Ψ 3 | 2 = 2
L
sin 2 (3πx/L) — 3 peaks, 2 interior nodes at x = L/3, 2L/3
|Ψ 4 | 2 = 2
L

|Ψ 5 | 2 = 2
L
∣
sin 2 (4πx/L) — 4 peaks, 3 interior nodes at x = L/4, L/2, 3L/4

sin 2 (5πx/L) — 5 peaks, 4 interior nodes at

x = L/5, 2L/5, 3L/5, 4L/5

Correspondence principle: As n → ∞, the peaks multiply and the

average value approaches 1/L uniformly — recovering the classical
result that a particle bouncing in a box is equally likely to be found
anywhere.

PROBLEM 2 Computing ⟨p 2x ⟩ and ⟨x 2 ⟩ for Ψ n

 For the particle in a box, consider Ψ n (x, t) and compute ⟨p 2x ⟩ and
⟨x 2 ⟩.

PART A — ⟨P2X⟩

The momentum-squared operator is p^2x = −ℏ 2 d 2 /dx 2 . The

expectation value is:

L
d2
⟨p 2x ⟩ =∫ ψ n (x)(−ℏ 2
)ψ n (x) dx
0 dx 2

We compute the second derivative of ψ n = √2/L sin(nπx/L):

d2 ψn n2 π2
= − 2 ψ n (x)
dx 2 L

Substituting (using ψ n real, so ψ ∗n = ψ n ):

n2 π2 ℏ 2 L n2 π2 ℏ 2
= ∫ |ψ n | dx =
2
⟨p 2x ⟩

  0  
L2 L2
= 1 (normalised)

RESULT

n2 π2 ℏ 2
⟨p 2x ⟩ = = 2mE n
L2
 p 2 ⟩/2m, giving
Check: Inside the box V = 0, so E n = ⟨^
⟨p 2x ⟩ = 2mE n . ✓

PART B — ⟨X2 ⟩

The expectation value is:

L
2
∫ x 2 sin 2 ( )dx
2 nπx
⟨x ⟩ =
L 0 L

Using the identity sin 2 θ = (1 − cos 2θ)/2:

2 1 L 2 1 L 2 2nπx
⟨x ⟩ = [ ∫ x dx −
2
∫ x cos( )dx]
L 2 0 2 0 L

First integral:

1 L 2 L3
∫ x dx =
2 0 6

L
Second integral — let I = ∫ x 2 cos( 2nLπx )dx , evaluated by
0
parts twice.

First integration by parts: u = x 2 , dv = cos(2nπx/L) dx:

 L L
xL ⋅ x 2nπx 2nπx
I=[ )] − )dx
L
sin( ∫ x sin(

   
2nπ L 0 nπ 0 L
= 0, since sin(2nπ)=0

Second integration by parts: u = x, dv = sin(2nπx/L) dx:

L L
2nπx 2nπx
)dx = [− )] +
L
∫ x sin(
xL
cos(



     
0 L 2nπ L 0 2nπ
= −L 2 /(2nπ)

2 2
At x = L: − 2nπ
L L . At = 0: 0. The remaining
cos(2nπ) = − 2nπ x
integral vanishes (complete period). So:

L
2nπx L2
∫ x sin( )dx = −
0 L 2nπ

Therefore:

L2 L3
⋅ (− )=
L
I=−
nπ 2nπ 2n 2 π 2

Assembling the full expression:

 2 L3 L3 1 1
⟨x ⟩ = [
2
− ] = 2L 2 [ − ]
L 6 4n 2 π 2 6 4n 2 π 2

RESULT

1 1
⟨x 2 ⟩ = L 2 ( − )
3 2n 2 π 2

Check (classical limit): As n → ∞, ⟨x 2 ⟩ → L 2 /3. For a uniform

L
classical distribution on [0, L]: ⟨x 2 ⟩ cl = ∫ 0 x 2 (1/L) dx = L 2 /3.
✓

PROBLEM 3 Is ∑ ∞
n=1
1 Ψ n a Physical Solution?
√n

Consider Φ(x, t) = ∑ ∞
n=1
1
Ψ n (x, t). Is it a physical solution?
√n

CRITERION FOR A PHYSICAL WAVEFUNCTION

A quantum state must be square-integrable and normalisable:

∫ |Φ| 2 dx must be !nite. For a general superposition Φ = ∑ n c n Ψ n
, using orthonormality of the eigenstates (∫ Ψ ∗m Ψ n dx = δ mn ):
 L L
∫ 2
|Φ(x, t)| dx = ∑ c ∗m c n ∫ Ψ ∗m Ψ n dx = ∑ c ∗m c n δ m
0 m,n 0 m,n

∞
Normalisability therefore requires ∑ |c n | 2 < ∞ (the sequence
n=1
{c n } must be square-summable, i.e., {c n } ∈ ℓ 2 ).

CHECKING THE PROPOSED SOLUTION

Here c n = 1/√n, so |c n | 2 = 1/n. The normalisability condition

becomes:

∞ ∞
1 1 1
∑ |c n | = ∑
2
=1+ + +⋯
n=1 n=1
n 2 3

This is the harmonic series. By the integral test:

N
1 N+1
∑ ≥ ∫
dx N→∞
− = ln(N + 1) → ∞
n=1 n 1 x

The harmonic series diverges.

CONCLUSION

Φ(x, t) is not normalisable since ∑ ∞

n=1
1/n = ∞. It does
not represent a valid physical quantum state.
 Contrast: If instead c n = 1/n, then
∑ |c n | 2 = ∑ 1/n 2 = π 2 /6 < ∞ — that would be physical
(after normalisation). The boundary between convergence and
divergence of ∑ n −p occurs at p = 1; the coe"cients c n = 1/√n
lie exactly at the divergent boundary.

PROBLEM 4 2D Rectangular Box — Separation of Variables

Find the wavefunctions and energy spectrum of the 2D box. What

happens when L 1 = L 2 ?

SETTING UP THE 2D TISE

Inside the box, the potential is zero and the 2D time-independent

Schrödinger equation is:

ℏ 2 ∂ 2ψ ∂ 2ψ
− ( + ) = E ψ(x, y)
2m ∂ x 2 ∂y2

with ψ = 0 on all four walls. The boundary conditions are:

ψ(± L21 , y) = 0, ψ(x, ± L22 ) = 0

SEPARATING THE VARIABLES

Assume a product ansatz ψ(x, y) = X(x) Y (y). Substituting and

dividing by XY :

ℏ 2 X ′′ ℏ 2 Y ′′
− + (− )=E
2m X 2m Y

The !rst term depends only on x and the second only on y, yet their
sum is a constant E. This is only possible if each term is separately
constant:

ℏ 2 ′′ ℏ 2 ′′
− X = E x X, − Y = Ey Y , Ex + Ey
2m 2m

The 2D problem decouples into two independent 1D particle-in-a-box

problems.

SOLVING THE 1D PROBLEMS (CENTRED BOX)

For the x-equation on [−L 1 /2, L 1 /2], the general solution is:

√2mE x
X(x) = A sin(k x x) + B cos(k x x), kx =
ℏ

Applying X(±L 1 /2) = 0:

 X(+L 1 /2) : A sin kx2L1 + B cos kx2L1 = 0

X(−L 1 /2) : −A sin kx2L1 + B cos kx2L1 = 0

Adding: 2B cos(k x L 1 /2) = 0. Subtracting:

2A sin(k x L 1 /2) = 0. Two families of solutions arise:

Symmetric (even) solutions — A = 0, cos(k x L 1 /2) = 0:

X nx (x) = √
nx π 2
kx = , n x = 1, 3, 5, … ⇒ cos
L1 L1

Antisymmetric (odd) solutions — B = 0, sin(k x L 1 /2) = 0:

X nx (x) = √
nx π 2
kx = , n x = 2, 4, 6, … ⇒ sin
L1 L1

Both families are indexed by n x = 1, 2, 3, … with separation energy

E x,nx = n 2x π 2 ℏ 2 /(2mL 21 ). The same analysis applies to Y with
n y = 1, 2, 3, …

FULL WAVEFUNCTIONS AND ENERGY SPECTRUM

The product wavefunctions are (the explicit form depends on parity of

n x and n y ):
 WAVEFUNCTIONS

2
f nx( )f ny( )
n x πx n y πy
ψ nx ,ny (x, y) =
√L 1 L 2 L1 L2

where f k (θ) = cos θ if k is odd and f k (θ) = sin θ if k is

even.

ENERGY SPECTRUM

n 2y
( ) ,
π 2 ℏ 2 n 2x
E nx ,ny = + n x , n y = 1, 2, 3, …
2m L 21 L 22

SPECIAL CASE: L1 = L2 = L ( S Q U A R E B O X )

The energy simpli!es to E nx ,ny = E 1 (n 2x + n 2y ) where

E 1 = π 2 ℏ 2 /(2mL 2 ). The energy depends only on the combination
n 2x + n 2y .

Whenever two distinct pairs (n x , n y ) and (n ′x , n ′y ) satisfy

n 2x + n 2y = n ′x2 + n ′y2 , they correspond to di!erent orthogonal
wavefunctions with the same energy — this is called degeneracy.

Examples of degenerate levels:

• (1, 2) and (2, 1): 1 2 + 2 2 = 5, 2-fold degenerate
• (1, 3) and (3, 1): 1 2 + 3 2 = 10, 2-fold degenerate
• (2, 2) alone: 2 2 + 2 2 = 8, non-degenerate
This degeneracy arises from the enhanced rotational symmetry of
the square box — the Hamiltonian is invariant under x ↔ y, so
states related by swapping n x ↔ n y must be degenerate.
 Superposition Ψ = 1 (Ψ 1 + Ψ 2 ) — Normalisation
PROBLEM 5
√2
& Periodicity

Show that Ψ(x, t) = 1 (Ψ 1 + Ψ 2 ) is normalised, plot |Ψ| 2 ,

√2
and show it is periodic.

PART A — PROVING NORMALISATION

Expand the modulus squared:

L
1 L ∗
∫ |Ψ| dx = ∫ (Ψ 1 + Ψ ∗2 )(Ψ 1 + Ψ 2 ) dx
2
0 2 0
L L L L
1
= [∫ |Ψ 1 | dx + ∫ |Ψ 2 | dx + ∫ Ψ 1 Ψ 2 dx + ∫
2 2 ∗
2 0 0 0 0

The cross terms are evaluated using orthonormality:

L
∫ Ψ ∗m Ψ n dx = e i(Em −En )t/ℏ δ mn .
0

1 1
= [δ 11 + δ 22 + δ 12 + δ 21 ] = [1 + 1 + 0 + 0] = 1 ✓
2 2

PART B — EXPLICIT FORM OF |Ψ(X, T)| 2

 =
1 2
2
|Ψ| 2 =

|Ψ(x, t)| 2 =
1
L
2

∣
Writing Ψ n = ψ n (x) e −iEn t/ℏ with real ψ n :

1
ψ 1 e −iE1 t/ℏ + ψ 2 e −iE2 t/ℏ

[sin 2

PART C — SHOWING PERIODICITY

ω 21 T = 2π:

PERIOD
ω 21 =

T=
E2 − E1
ℏ

2π
ω 21
=
πx
L

=
+ sin 2

2mL 2
2πx
L
+ 2 sin

The only time-dependent factor is cos(ω 21 t) with:

(4 − 1)π 2 ℏ
=
3π 2 ℏ
2mL 2
πx
L
sin

The probability density returns to its initial value whenever

2πℏ
E2 − E1
=
4mL 2
3πℏ
2

[ψ 1 + ψ 22 + ψ 1 ψ 2 (e i(E1 −E2 )t/ℏ + e −i(E1 −E2 )t/ℏ )]

Applying Euler's formula e iθ + e −iθ = 2 cos θ:

PROBABILITY DENSITY

2πx
L
⋅ cos
The plot below shows |Ψ(x, t)| 2 at four moments across one period,
showing the probability "sloshing" back and forth.

|Ψ(x, t)| 2 at t = 0 (blue), t = T /4 (teal), t = T /2 (orange), t = 3T /4

(pink) — probability density oscillates with period T

PROBLEM 6 Periodicity of the General n-State Superposition

∑ ni=1 c i Ψ i (x, t)
Show that Ψ(x, t) = is periodic in time.
√∑ ni=1 |c i | 2

NORMALISED FORM

Let N 2 = ∑ ni=1 |c i | 2 and de!ne normalised coe"cients

c~i = c i /N , so ∑ i |c~i | 2 = 1. Then:

n
Ψ(x, t) = ∑ c~i ψ i (x) e −iEi t/ℏ
i=1
 COMPUTING |Ψ(X, T)| 2

Taking the modulus squared by multiplying Ψ ∗ ⋅ Ψ:

n n
|Ψ(x, t)| = ∑ ∑ c~i c~∗j ψ i (x) ψ j (x) e −i(Ei −Ej )t/ℏ
2

i=1 j=1

Splitting into diagonal and o$-diagonal parts:

n n
|Ψ(x, t)| = 2
∑ |c~i | 2 ψ 2i (x) + ∑ c~i c~∗j ψ i ψ j e −iωij t

   
i=1 i,j=1

   
i≠j
static (time-independent)
oscillatory terms

where the transition frequency between levels i and j is

ω ij = (E i − E j )/ℏ.

KEY: ALL FREQUENCIES ARE COMMENSURATE FOR THE INFINITE

SQUARE WELL

For the particle in a box, E n = n 2 E 1 (energies scale as n 2 ).

Therefore:

Ei − Ej (i 2 − j 2 )E 1
ω ij = = = (i 2 − j 2 ) ω 1 , ω1 ≡
ℏ ℏ

Every transition frequency is an integer multiple of the fundamental

frequency ω 1 . This is the crucial mathematical condition for
periodicity.

PROVING |Ψ(X, T)| 2 I S P E R I O D I C W I T H P E R I O D T = 2Π/Ω1

De!ne T ≡ 2π/ω 1 . We show |Ψ(x, t + T )| 2 = |Ψ(x, t)| 2 .

For every oscillatory term, evaluate the time-shift:

2 −j 2
e −iωij (t+T ) = e −iωij t ⋅ e −iωij T = e −iωij t ⋅ e −i(i )ω 1 ⋅(2π/ω 1 )

2 −j 2
= e −iωij t ⋅ e −2πi(i )

Since i 2 − j 2 is an integer, and e −2πi k = 1 for any integer k:

e −iωij (t+T ) = e −iωij t ⋅ 1 = e −iωij t

Every term in the double sum is invariant under t → t + T , so the

entire expression satis!es:

CONCLUSION

2πℏ 4
|Ψ(x, t + T )| 2 = |Ψ(x, t)| 2 ∀ x, t with T = =
E1

The probability density of any !nite linear combination of

stationary states of the in!nite square well is periodic in time.
■
 Why this is special to the in!nite square well: The quadratic
energy spectrum E n = n 2 E 1 makes all transition frequencies
integer multiples of ω 1 , guaranteeing a common period. For a
generic potential (e.g., a harmonic oscillator has linear spacing
E n ∝ n, or an anharmonic oscillator), the transition frequencies
may be irrational multiples of each other, and the superposition may
be quasi-periodic rather than strictly periodic.

IISER Bhopal · Quantum Physics (2026) · Detailed solutions for

Post Mid-sem Assignment II