Quantum Chemistry – Solution set 3

1. Hermitian operators cont’d.

2. The Hamiltonian
3. Measured and average values
4. Schrödinger equation
a. Time dependent
b. Time independent
5. Example: A particle in a box

1. Hermitian operators cont’d :

i. ̂ and 𝑩
𝑨 ̂ are Hermitian, and [𝑨 ̂, 𝑩
̂ ] = 𝟎. Show that there is a complete
set of function that are eigenfunctions of both 𝑨 ̂ and 𝑩̂.
You may neglect the case of degenerate eigenfunctions.
̂, 𝑩
Also show that if [𝑨 ̂ ] ≠ 𝟎 a joint complete set doesn’t exist.

 To fully complete the proof, you should also refer to the case of
degenerate eigenfunction and use the previous knowledge that the
eigenfunctions of any Hermitian operator is a complete set.

 You should also show specifically that it doesn't work in the case
̂, 𝑩
[𝑨 ̂] ≠ 𝟎
o Given [𝑨 ̂ ] ≠ 𝟎, assume 𝜓 is an e.f of both 𝐴̂, 𝐵̂
̂, 𝑩
o Therefore: 𝐵̂𝐴̂𝜓 = 𝑎𝐵̂𝜓 = 𝑎𝑏𝜓
o And: 𝐴̂𝐵̂𝜓 = 𝑏𝐴̂𝜓 = 𝑏𝑎𝜓 = 𝑎𝑏𝜓 = 𝐵̂𝐴̂𝜓
o If this is true for any 𝜓 then 𝐴𝐵 = 𝐵𝐴
o Which is in contradiction with [𝑨 ̂, 𝑩
̂] ≠ 𝟎
o so the assumption that 𝜓 is an e.f of both 𝐴̂, 𝐵̂ is wrong.

ii. Prove that if a Hermitian operator has two linearly independent

degenerate eigenvectors (with the same eigenvalue) they can be
orthogonalised.
 If 𝜓, 𝜙 are both eigenvectors of 𝐴, with the same eigenvalue, 𝑎:
𝐴𝜓 = 𝑎𝜓 and 𝐴𝜙 = 𝑎𝜙
But for no 𝛼, 𝛽 does 𝛼𝜓 + 𝛽𝜙 = 0.
We can build an orthogonal eigenvector to 𝜓.
First we notice that for any 𝛼, 𝛽
𝛼𝜓 + 𝛽𝜙
Is also an eigenvector of 𝐴 with eigenvalue 𝑎:
𝐴(𝛼𝜓 + 𝛽𝜙) = 𝛼𝐴𝜓 + 𝛽𝐴𝜙 = 𝛼𝑎𝜓 + 𝛽𝑎𝜙 = 𝑎(𝛼𝜓 + 𝛽𝜙)
So we need to choose 𝛼, 𝛽 such that:
∫ 𝜓∗ (𝛼𝜓 + 𝛽𝜙)𝑑𝑥 = 0
𝛼∫ 𝜓 ∗ 𝜓𝑑𝑥 + 𝛽∫ 𝜓 ∗ 𝜙𝑑𝑥 = 0

Which means:
𝛼 ∫ 𝜓 ∗ 𝜙𝑑𝑥
=−
𝛽 ∫ 𝜓 ∗ 𝜓𝑑𝑥
1. Add an explicit example ( 𝑒 𝑖𝑘𝑥 ) and maybe vectors

̂ ):
2. The Hamiltonian (ℋ
The operator representing the total energy
ℋ̂ = 𝑇̂ + 𝑉̂ (𝑥)
A system is specified by its potential and its boundary conditions.
E.g. a Quantum harmonic oscillator: 𝓗 ̂=𝑻 ̂ +𝒌𝒙 ̂𝟐
𝟐

a) Prove that by choosing the appropriate value of 𝛼, 𝜓0 (𝑥) = exp(−𝛼𝑥 2 )

satisfies the relation ℋ̂ 𝜓0 = 𝐸𝜓0 where 𝐸 is a constant. What is the value of 𝛼
to maintain this relation? What is the value of 𝐸?
𝐻𝜓0 (𝑥) = 𝐸0 𝜓0 (𝑥)
ℏ2 𝑑2 𝑘
[− 2
+ 𝑥 2 ] 𝜓0 (𝑥) = 𝐸0 𝜓0 (𝑥)
2𝑚 𝑑𝑥 2

ℏ2 𝑑2 𝑘
− 2
𝜓0 (𝑥) + 𝑥 2 𝜓0 (𝑥) = 𝐸0 𝜓0 (𝑥)
2𝑚 𝑑𝑥 2
2
𝜓0 (𝑥) = 𝑒 −𝛼𝑥
ℏ2 𝑘
− [−2𝛼𝜓0 (𝑥) + 4𝛼 2 𝑥 2 𝜓0 (𝑥)] + 𝑥 2 𝜓0 (𝑥) = 𝐸0 𝜓0 (𝑥)
2𝑚 2
ℏ2 ℏ2 𝑘
( 2𝛼) 𝜓0 (𝑥) + (− 4𝛼 2 + ) 𝑥 2 𝜓0 (𝑥) = 𝐸0 𝜓0 (𝑥)
2𝑚 2𝑚 2

ℏ2 𝑘
− 4𝛼 2 + = 0
2𝑚 2
√𝑘𝑚
𝛼=
2ℏ
 ℏ2 ℏ2 √𝑘𝑚 ℏ 𝑘 ℏ𝜔
𝐸0 = 2𝛼 = 2 = √ =
2𝑚 2𝑚 2ℏ 2 𝑚 2

b) Show that 𝜓1 (𝑥) = 𝑥𝜓0 (𝑥) holds this relation as well.

What is 𝐸1 ?
𝐻𝜓1 (𝑥) = 𝐸1 𝜓1 (𝑥)
2 2
ℏ 𝑑 𝑘
− 𝜓 (𝑥) + 𝑥 2 𝜓1 (𝑥) = 𝐸1 𝜓1 (𝑥)
2𝑚 𝑑𝑥 2 1 2
ℏ2 𝑑2 𝑘 3
− [𝑥𝜓 0 (𝑥)] + 𝑥 𝜓0 (𝑥) = 𝐸1 𝑥𝜓0 (𝑥)
2𝑚 𝑑𝑥 2 2
ℏ2 𝑑 𝑑2 𝑘
− [2 𝜓0 (𝑥) + 𝑥 2 𝜓0 (𝑥)] + 𝑥 3 𝜓0 (𝑥) = 𝐸1 𝑥𝜓0 (𝑥)
2𝑚 𝑑𝑥 𝑑𝑥 2
2
𝜓0 (𝑥) = 𝑒 −𝛼𝑥
ℏ2 𝑘
− [2(−2𝛼𝑥)𝜓0 (𝑥) + 𝑥(−2𝛼 + 4𝛼 2 𝑥 2 )𝜓0 (𝑥)] + 𝑥 3 𝜓0 (𝑥) = 𝐸1 𝑥 𝜓0 (𝑥)
2𝑚 2
ℏ2 ℏ2 𝑘
− (−6𝛼)𝑥𝜓0 (𝑥) + [− 4𝛼 2 + ] 𝑥 3 𝜓0 (𝑥) = 𝐸1 𝑥 𝜓0 (𝑥)
2𝑚 2𝑚 2

ℏ2 𝑘
− 4𝛼 2 + = 0
2𝑚 2
√𝑘𝑚
𝛼=
2ℏ

ℏ2 ℏ2 √𝑘𝑚 3 𝑘 3
𝐸1 = 6𝛼 = 6 = ℏ√ = ℏ𝜔
2𝑚 2𝑚 2ℏ 2 𝑚 2

c) Show that 𝜓2 (𝑥) = (𝑥 2 − 𝛽)𝜓0 (𝑥) holds this relation as well.

What are 𝛽 and 𝐸2 ?
𝐻𝜓2 (𝑥) = 𝐸2 𝜓2 (𝑥)
ℏ2 𝑑2 𝑘
− 2
𝜓2 (𝑥) + 𝑥 2 𝜓2 (𝑥) = 𝐸2 𝜓2 (𝑥)
2𝑚 𝑑𝑥 2
ℏ2 𝑑2 𝑘
− 2
[(𝑥 2 − 𝛽)𝜓0 (𝑥)] + 𝑥 2 (𝑥 2 − 𝛽)𝜓0 (𝑥) = 𝐸2 (𝑥 2 − 𝛽)𝜓0 (𝑥)
2𝑚 𝑑𝑥 2
ℏ2
− [(2𝜓0 (𝑥) + 2𝑥(−2𝛼𝑥)𝜓0 (𝑥) − 6𝛼𝑥 2 𝜓0 (𝑥) − 2𝛼𝑥 3 (−2𝛼𝑥)𝜓0 (𝑥)) − 𝛽(−2𝛼 + 4𝛼 2 𝑥 2 )𝜓0 (𝑥)]
2𝑚
𝑘
+ 𝑥 2 (𝑥 2 − 𝛽)𝜓0 (𝑥) = 𝐸2 (𝑥 2 − 𝛽)𝜓0 (𝑥)
2
ℏ2 ℏ2 ℏ2 𝑘 ℏ2 𝑘
− 2(1 + 𝛽𝛼)𝜓0 (𝑥) + ( 10𝛼 − 4𝛼 2 𝛽 + 𝛽) 𝑥 2 𝜓0 (𝑥) + (− 4𝛼 2 + ) 𝑥 4 𝜓0 (𝑥)
2𝑚 2𝑚 2𝑚 2 2𝑚 2
2
= 𝐸2 (𝑥 − 𝛽)𝜓0 (𝑥)
Again:
 ℏ2 𝑘
− 4𝛼 2 + = 0
2𝑚 2
√𝑘𝑚
𝛼=
2ℏ
Equating the coefficients of 𝑥 2 𝜓0 (𝑥) to find 𝐸2 :

ℏ2 ℏ2 𝑘
𝐸2 = ( 10𝛼 − 4𝛼 2 𝛽 + 𝛽)
2𝑚 2𝑚 2
ℏ2 ℏ2 𝑘
= 10𝛼 + 𝛽 (− 4𝛼 2 + )
2𝑚 2𝑚 2
ℏ2 ℏ2 √𝑘𝑚 5 𝑘
= 10𝛼 = 10 = ℏ√
2𝑚 2𝑚 2ℏ 2 𝑚

𝟓
𝑬𝟐 = ℏ𝝎
𝟐
To find 𝛽:
ℏ2
− 2(1 + 𝛽𝛼) = −𝛽𝐸2
2𝑚
ℏ2 ℏ2
− = ( 𝛼 − 𝐸2 ) 𝛽
𝑚 𝑚
1 1 ℏ
𝛽= = =
𝐸2 𝑚
− 𝛼 5 √𝑘𝑚 − √𝑘𝑚 2√𝑘𝑚
ℏ2 2 ℏ 2ℏ
We can verify that 𝛽 has units of area, as required by the definition of 𝜓2 (𝑥).

d) Show that 𝜓3 (𝑥) = (𝑥 3 − 𝛾𝑥)𝜓0 (𝑥) holds this relation as well.

What are 𝛾 and 𝐸3 ?

𝐻𝜓3 (𝑥) = 𝐸3 𝜓3 (𝑥)

2 2
ℏ 𝑑 𝑘
− 2
𝜓3 (𝑥) + 𝑥 2 𝜓3 (𝑥) = 𝐸3 𝜓3 (𝑥)
2𝑚 𝑑𝑥 2
ℏ2 𝑑 2 𝑘
− [(𝑥 3 − 𝛾𝑥)𝜓0 (𝑥)] + 𝑥 2 (𝑥 3 − 𝛾𝑥)𝜓0 (𝑥) = 𝐸3 (𝑥 3 − 𝛾𝑥)𝜓0 (𝑥)
2𝑚 𝑑𝑥 2 2
ℏ2 𝑘 𝑘
− [6(1 + 𝛼𝛾)𝑥𝜓 + (−14𝛼 − 4𝛼𝛾)𝑥 3 𝜓 + (4𝛼 2 )𝑥 5 𝜓] + 𝑥 5 𝜓0 (𝑥) − 𝛾𝑥 3 𝜓0 (𝑥)
2𝑚 2 2
= 𝐸3 (𝑥 3 − 𝛾𝑥)𝜓0 (𝑥)

ℏ2 ℏ2 𝑘 ℏ2 𝑘
− 6(1 + 𝛼𝛾)𝑥𝜓 + [− (−14𝛼 − 4𝛼𝛾) − 𝛾] 𝑥 3 𝜓 + (− (4𝛼 2 ) + ) 𝑥 5 𝜓0 (𝑥)
2𝑚 2𝑚 2 2𝑚 2
3
= 𝐸3 (𝑥 − 𝛾𝑥)𝜓0 (𝑥)

Again:
ℏ2 𝑘
− (4𝛼 2 ) + = 0
2𝑚 2
 √𝑘𝑚
𝛼=
2ℏ

ℏ2 ℏ2 𝑘
𝐸3 = 14𝛼 + ( 4𝛼 − ) 𝛾
2𝑚 2𝑚 2
ℏ2 ℏ2 √𝑘𝑚 7 𝑘
= 14𝛼 = 14 = ℏ√
2𝑚 2𝑚 2ℏ 2 𝑚

𝟕
𝑬𝟑 = ℏ𝝎
𝟐
And to find 𝛾:
ℏ2
−6(1 + 𝛼𝛾) = −𝛾𝐸3
2𝑚
ℏ2 ℏ2
− 6=( 6𝛼 − 𝐸3 ) 𝛾
2𝑚 2𝑚
1 1 3ℏ
𝛾= = =
𝑚𝐸3 𝑚 7 √ 𝑘 √𝑘𝑚 2√𝑘𝑚
−𝛼 ℏ −
3ℏ2 3ℏ2 2 𝑚 2ℏ
And again we can verify that 𝛾 has units of area, as required by the definition of
𝜓3 (𝑥).

3. Measured and average values

Postulate:
i. The result of a single measurement of a physical observable represented by
operator 𝐴̂ can only be an eigenvalue of 𝐴̂
ii. If the state of the particle is described by the normalized wave function
𝜓(𝑥, 𝑡) = ∑ 𝑐𝑛 𝜙𝑛 (𝑥, 𝑡)
𝑛
Where 𝜙𝑛 (𝑥, 𝑡) is an eigenfunction of 𝐴̂ with the eigenvalue 𝑎𝑛 , then the
probability that the outcome of a single measurement will be 𝑎𝑛 is |𝑐𝑛 |2
iii. The average value of many measurements of 𝐴̂ in this case is the expectation
value of the operator:
〈𝐴̂〉 = ∫ 𝜓(𝑥, 𝑡)∗ 𝐴̂𝜓(𝑥, 𝑡)𝑑𝑥
Since we normalized:
∫ 𝜓(𝑥, 𝑡)∗ 𝐴̂𝜓(𝑥, 𝑡)
〈𝐴̂〉 = 𝑑𝑥
∫ 𝜓(𝑥, 𝑡)∗ 𝜓(𝑥, 𝑡)

iv. The overlap between any two normalized states 𝜙𝑛 and 𝜓 is their inner product
𝐶𝑛 = ∫ 𝜙𝑛 (𝑥, 𝑡)∗ 𝜓(𝑥, 𝑡)𝑑𝑥 and the probability to measure 𝜙𝑛 (𝑥, 𝑡) given the case
we are at the state 𝜓(𝑥, 𝑡) is |𝑐𝑛 |2
a) If 𝝍(𝒙, 𝒕) = ∑𝒏 𝒄𝒏 𝝓𝒏 (𝒙, 𝒕) is a non-normalized function, where 𝝓𝒏 (𝒙, 𝒕) are a
set of orthogonal eigenfunctions. Prove that the Normalization factor
𝟏
𝑵 = √∑ 𝟐
𝒏|𝒄𝒏 |

𝑁 2 ∫ 𝜓(𝑥, 𝑡)∗ 𝜓(𝑥, 𝑡)𝑑𝑥 = 1

∗

𝑁 2 ∫ (∑ 𝑐𝑛 𝜙𝑛 (𝑥, 𝑡)) (∑ 𝑐𝑚 𝜙𝑚 (𝑥, 𝑡)) 𝑑𝑥

𝑛 𝑚
= 𝑁 ∑ ∑ 𝑐𝑛∗ 𝑐𝑚 ∫ 𝜙𝑛∗ (𝑥, 𝑡) 𝜙𝑚 (𝑥, 𝑡)𝑑𝑥 = 𝑁 2 ∑ ∑ 𝑐𝑛∗ 𝑐𝑚 𝛿𝑛𝑚
2

𝑛 𝑚 𝑛 𝑚
2
=𝑁 ∑ 𝑐𝑛∗ 𝑐𝑛 2
= 𝑁 ∑|𝑐𝑛 |2 =1
𝑛 𝑛
So:
𝟏
𝑵=√
∑𝒏|𝒄𝒏 |𝟐
b) For a Hermitian operator 𝑨 ̂ , with normalized eigenfunctions 𝝋𝒏 and
eigenvalues 𝒂𝒏 ,
prove:
〈𝐴̂〉 = ∫ 𝜓(𝑥, 𝑡)∗ 𝐴̂𝜓(𝑥, 𝑡)𝑑𝑥 = ∑|𝑐𝑛 |2 𝑎𝑛
𝑛
𝐴̂ is Hermitian so its eigenfunctions, 𝜑𝑛 , (such that 𝐴𝜑𝑛 = 𝑎𝑛 𝜑𝑛 ) can span
the entire space. Therefore we can write:
𝜓(𝑥, 𝑡) = ∑ 𝑐𝑛 𝜑𝑛 (𝑥, 𝑡)
𝑛
Substituting into the above relation. We choose 𝑐𝑛 such that 𝜓(𝑥) is a
normalized eigenfunction.
∗

∫ 𝜓(𝑥, 𝑡) 𝐴̂𝜓(𝑥, 𝑡)𝑑𝑥 = ∫ (∑ 𝑐𝑛 𝜑𝑛 (𝑥, 𝑡)) 𝐴̂ (∑ 𝑐𝑚 𝜑𝑚 (𝑥, 𝑡)) 𝑑𝑥

∗

𝑛 𝑚
using the linearity of 𝐴̂ and working out the conjugation:

= ∫ ∑ 𝑐𝑛∗ 𝜑𝑛∗ (𝑥, 𝑡) (∑ 𝑐𝑚 𝐴̂𝜑𝑚 (𝑥, 𝑡)) 𝑑𝑥

𝑛 𝑚
Applying the eigenvalue relation:
= ∫ ∑ 𝑐𝑛∗ 𝜑𝑛∗ (𝑥, 𝑡) ∑ 𝑐𝑚 𝑎𝑚 𝜑𝑚 (𝑥, 𝑡) 𝑑𝑥
𝑛 𝑚
changing the order of summation and integration:
= ∑ 𝑎𝑚 𝑐𝑛∗ 𝑐𝑚 ∫ 𝜑𝑛∗ (𝑥, 𝑡)𝜑𝑚 (𝑥, 𝑡)𝑑𝑥
𝑛,𝑚
using the orthogonality of the eigenfunctions of 𝐴̂ (and the fact they are
normalized):
= ∑ 𝑎𝑚 𝑐𝑛∗ 𝑐𝑚 𝛿𝑛𝑚
𝑛,𝑚=0
0, 𝑛 ≠ 𝑚
Since 𝛿𝑛𝑚 = { most of the terms fall, only the terms that satisfy
1, 𝑛 = 𝑚
𝑛 = 𝑚 remain:
= ∑ 𝑎𝑛 𝑐𝑛∗ 𝑐𝑛 = ∑|𝑐𝑛 |2 𝑎𝑛
𝑛 𝑛
4. The Schrödinger equation
Postulate:
The state of a quantum system is propagated according to the Schrödinger equation,
a second order, partial deferential equation:
𝜕
ℋ ̂ 𝜓(𝑥, 𝑡) = 𝑖ℏ 𝜓(𝑥, 𝑡)
𝜕𝑡
2
i. Solve the Schrödinger eq. for the case that ̂ = 𝑝̂ + 𝑉(𝑥, 𝑡) is
ℋ 2𝑚
2
̂ = 𝑝̂ + 𝑉(𝑥).
independent of time, ℋ 2𝑚
𝜕
̂ 𝜓(𝑥, 𝑡) = 𝑖ℏ
ℋ 𝜓(𝑥, 𝑡)
𝜕𝑡
If 𝑉(𝑥, 𝑡) → 𝑉(𝑥) then we can rewrite 𝜓(𝑥, 𝑡) = 𝜓(𝑥)𝜓(𝑡)
𝜕
ℋ̂ 𝜓(𝑥)𝜓(𝑡) = 𝑖ℏ 𝜓(𝑥)𝜓(𝑡)
𝜕𝑡
1 1 𝜕
ℋ̂ 𝜓(𝑥) = 𝑖ℏ 𝜓(𝑡)
𝜓(𝑥) 𝜓(𝑡) 𝜕𝑡
1 𝜕
𝐸 = 𝑖ℏ 𝜓(𝑡)
𝜓(𝑡) 𝜕𝑡
𝜕
𝑖ℏ 𝜓(𝑡) = 𝐸𝜓(𝑡)
𝜕𝑡
Separation of variables:
𝑑𝜓(𝑡) 𝑖
= − 𝐸𝑑𝑡
𝜓(𝑡) ℏ
Integrate:
𝑖
ln 𝜓(𝑡) = − 𝐸𝑡
ℏ
𝑖𝐸
𝜓(𝑡) = 𝑒 − ℏ 𝑡
So:
𝑖𝐸
− 𝑡
𝜓(𝑥, 𝑡) = 𝜓(𝑥)𝑒 ℏ

When 𝓗 is independent of time we can use Time independent Schrödinger

equation:
𝓗𝝍𝒏 (𝒙, 𝒕) = 𝑬𝒏 𝝍𝒏 (𝒙, 𝒕)
and propagate each eigenfunction
𝒊𝑬𝒏
𝝍𝒏 (𝒙, 𝒕) = 𝐞𝐱𝐩(− 𝒕)𝝍𝒏 (𝒙, 𝒕 = 𝟎)
ℏ

5. Example: A particle in a box

A particle of mass 𝑚 is confined to a 1D box by the
0 ; 0≤𝑥≤𝐿
following potential 𝑉(𝑥) = {
∞ ; 𝑥 > 𝐿; 𝑥 < 0
2 𝑛𝜋
a) Show that 𝜓𝑛 = √𝐿 𝑠𝑖𝑛 ( 𝐿 𝑥), where 𝑛 = 1,2, … are
the eigenfunctions of the Hamiltonian (normalized)
Use the booklet by Ed Montgomery available on
Moodle: Topic 4 – Particle in a Box (pages 23-25)

We start from the time independent Schrodinger eq. (TISE):

𝐻𝜓(𝑥) = 𝐸𝜓(𝑥)
Where:
ℏ 𝑑2
𝐻 =𝑇+𝑉 =− + 𝑉(𝑥)
2𝑚 𝑑𝑥 2
So the TISE is:
ℏ 𝑑2
− 𝜓(𝑥) + 𝑉(𝑥)𝜓(𝑥) = 𝐸𝜓(𝑥)
2𝑚 𝑑𝑥 2
2𝑚
Multiplying by − ℏ and rearranging:
𝑑2 2𝑚
2
𝜓(𝑥) = (𝑉(𝑥) − 𝐸)𝜓(𝑥)
𝑑𝑥 ℏ
Now we need to look at the problem in the different areas where it is defined, to
find out what is the solution for the wavefunction.
Outside the box
When 𝑥 < 0 or when 𝑥 > 𝐿 we have 𝑉(𝑥) = ∞ so:
𝑑2 2𝑚
2
𝜓(𝑥) = (∞ − 𝐸)𝜓(𝑥) = ∞𝜓(𝑥)
𝑑𝑥 ℏ
Or:
1 𝑑2
𝜓(𝑥) = 0 = 𝜓(𝑥)
∞ 𝑑𝑥 2
Which means that outside the box the wavefunction is zero.
Inside the box
When 0 < 𝑥 < 𝐿 we have 𝑉(𝑥) = 0 so:
𝑑2 2𝑚 2𝑚
2
𝜓(𝑥) = (0 − 𝐸)𝜓(𝑥) = − 𝐸𝜓(𝑥)
𝑑𝑥 ℏ ℏ
Which we can rewrite:
𝑑2
𝜓(𝑥) = −𝜔2 𝜓(𝑥)
𝑑𝑥 2
Where we have defined:
2𝑚𝐸
𝜔2 =
ℏ
Which means:
2𝑚𝐸
𝜔=√
ℏ
And we can deduce that 𝜔 ≥ 0 as 𝐸 is the e.v of the kinetic energy inside the
box, and kinetic energy is always ≥ 0.
Solving the differential eq.
The question is what type of function, when you take its 2nd derivative, gives
back the same function multiplied by a negative factor? And what will that
factor be?

The answer is 𝑠𝑖𝑛 and 𝑐𝑜𝑠.

We write a general solution as a linear combination of them both:
𝜓(𝑥) = 𝐶1 cos(𝜔𝑥) + 𝐶2 sin(𝜔𝑥)
𝑑2
(You can verify that this general equation obeys 𝑑𝑥 2 𝜓(𝑥) = −𝜔2 𝜓(𝑥) )

Now we need to find 𝐶1 , 𝐶2 and 𝜔 according to the boundary conditions of the

problem.
At 𝑥 = 0, 𝜓(𝑥 = 0) = 0
(because 𝜓 has to be smooth. If for 𝑥 < 0, 𝜓 is 0 then it must equal to 0 also at
𝑥 = 0).
This means that:
𝜓(0) = 𝐶1 cos(0) + 𝐶2 sin(0) = 0
Since sin(0) = 0 then 𝐶1 must be 0.
 At 𝑥 = 𝐿, 𝜓(𝑥 = 𝐿) = 0
(because 𝜓 has to be smooth. If for 𝑥 > 𝐿, 𝜓 is 0 then it must equal to 0 also at
𝑥 = 𝐿).
This means that:
𝜓(𝐿) = sin(𝜔𝐿) = 0
𝑛𝜋
Since sin(𝜔𝐿) = 0 then 𝜔𝐿 = 𝑛𝜋 → 𝜔 = 𝐿 , 𝑛 = 0, ±1, ±2, ….
So:
𝑛𝜋𝑥
𝜓𝑛 (𝑥) = 𝐶2 sin ( ) , 𝑛 = 0, ±1, ±2, ….
𝐿
The next step is to check whether all values on 𝑛 are in agreement with the
solution of the differential equation.
For 𝒏 = 𝟎:
𝑑2
𝜓(𝑥) = 0
𝑑𝑥 2
The solution of this differential equation is not a 𝑠𝑖𝑛 or 𝑐𝑜𝑠 function, but a linear
function with 𝑥: 𝜓(𝑥) = 𝐴𝑥 + 𝐵 (which is the most general expression for which
𝑑2
𝑑𝑥 2
𝜓(𝑥)= 0 ) and when implying the boundary condition that 𝜓(0) = 𝜓(𝐿) = 0
means that 𝐴 = 𝐵 = 0 (you can verify this).
So 𝑛 = 0 needs to be excluded.
Negative 𝒏:
𝑛𝜋𝑥 𝑛𝜋𝑥
Since 𝜓−𝑛 (𝑥) = 𝐶2 𝑠𝑖𝑛 (− ) = − 𝐶2 𝑠𝑖𝑛 ( ) = −𝜓𝑛 (𝑥)
𝐿 𝐿
And the fact that in the boundaries of the box (0 < 𝑥 < 𝐿 ) |𝜓𝑛 (𝑥)|2 = |𝜓−𝑛 (𝑥)|2
Then these 2 functions actually represent the same solution.
So we can exclude negative or positive 𝑛 values (and we choose positive).

To find 𝐶2 we can use normalization like in Ex. Sheet 2

b) Find the eigenvalues 𝐸𝑛 of the Hamiltonian

2 2 2 2 2
Applying the Hamiltonian ℋ̂ = 𝑇̂ = − ℏ 𝑑 2 we can verify that 𝐸𝑛 = ℏ 𝑛 𝜋2
2𝑚 𝑑𝑥 2𝑚𝐿
c) What is the minimal energy that can be measured in the system?
ℏ2 𝜋2
The minimal value for 𝑛 = 1 ,𝐸1 = 2𝑚𝐿2, the fact that the particle is confined
force it to have minimum energy ( zero point energy)
d) Are the eigenfunctions degenerate?
No
e) Find the absorption spectrum that corresponds only to energetically adjacent
states for this system
ℏ2 𝜋 2 2 2)
ℏ2 𝜋 2
ℎ𝜈 = Δ𝐸 = 𝐸𝑛 − 𝐸𝑛−1 = (𝑛 (𝑛
− − 1) = (2𝑛 − 1)
2𝑚𝐿2 2𝑚𝐿2

f) Discuss the following limits 𝑚 → ∞, 𝐿 → ∞

Both limits reflect continuous energy values and 𝐸1 = 0 classical limit (Bohr
Correspondence principle)