Wave Function: Quantum Chemistry - Exercise Set 2
Wave Function: Quantum Chemistry - Exercise Set 2
Wave Function: Quantum Chemistry - Exercise Set 2
1. Wave functions
2. Operators
3. Eigenfunctions and eigenvalues
4. Hermitian operators
5. Other problems
6. Integrals
1. Wave function
Postulate 1: The state of a system is specified completely by a continuous
square-integrable wave function 𝝍. The 1-particle quantity |𝝍|𝟐 𝒅𝒓 is the
probability of finding the particle in a volume element 𝒅𝒓.
2
𝑁=√
𝑎
𝑎
b. What is the probability of finding the particle in the region [0, 2 ]
𝑎/2 𝑎/2
2 2 𝑛𝜋𝑥
𝑃=∫ |𝜓(𝑥, 𝑡 = 0)|2 𝑑𝑥 = ∫ sin ( ) 𝑑𝑥
0 0 𝑎 𝑎
𝑎
𝑎 𝑛𝜋𝑥 𝑎 𝑛𝜋𝑥 2
2 21− 𝑐𝑜𝑠 (2 𝑎 ) 2 𝑥 2 𝑠𝑖𝑛 (2 𝑎 ) 1
= ∫ 𝑑𝑥 = [ ] −[ ] =
𝑎 0 2 𝑎 20 2𝜋 2
2 𝑎
( 0)
∞
We demand ∫ |𝜓(𝑥, 𝑡 = 0)|2 𝑑𝑥 = ∫−∞ 𝑁 2 exp(−2𝛼𝑥 2 ) 𝑑𝑥 = ⋯ =
1
2 𝜋 2𝛼 4
𝑁 √2𝛼 = 1 the final answer is 𝑁 = (𝜋)
d. For the free 1-D particle, find an expression for the probability of finding it in
the region [𝑎, 𝑏] at time 𝑡 = 0.
𝑏 𝑏
2𝛼
𝑃 = ∫ |𝜓(𝑥, 𝑡 = 0)|2 𝑑𝑥 = ∫ √ exp(−2𝛼𝑥 2 ) 𝑑𝑥
𝑎 𝑎 𝜋
𝑑𝑦
𝑦 = √2𝛼𝑥, 𝑦 2 = 2𝛼𝑥 2 , 𝑑𝑥 =
√2𝛼
𝑏√2𝛼
1
𝑃=∫ exp(−𝑦 2 ) 𝑑𝑦
𝑎√2𝛼 √𝜋
𝑏√2𝛼 𝑎√2𝛼
1 1
=∫ exp(−𝑦 2 ) 𝑑𝑦 − ∫ exp(−𝑦 2 ) 𝑑𝑦
0 √ 𝜋 0 √ 𝜋
1
= [erf(𝑏√2𝑏) − erf(𝑎√2𝑏)]
2
2. Operators:
a. General algebra
Operation
Equal 𝐴̂ = 𝐵̂ 𝐴̂𝑓(𝑥) = 𝐵̂𝑓(𝑥) For any function 𝑓(𝑥)
Product by a scalar (𝛼𝐴̂)𝑓(𝑥) = 𝛼 (𝐴̂𝑓(𝑥))
Sum (𝐴̂ + 𝐵̂)𝑓(𝑥) = 𝐴̂𝑓(𝑥) + 𝐵̂𝑓(𝑥)
product (𝐴̂𝐵̂)𝑓(𝑥) = 𝐴̂ (𝐵̂𝑓(𝑥))
power
𝐴̂𝑛 𝑓(𝑥) = 𝐴̂ (𝐴̂ (… (𝐴̂𝑓(𝑥))))
b. Linear operators:
Definition of Linear operator 𝐴̂(𝛼𝑓(𝑥) + 𝛽𝑔(𝑥)) = 𝛼𝐴̂𝑓(𝑥) + 𝛽𝐴̂𝑔(𝑥)
I. 𝐴̂1 = 𝛾𝑥̂
Linear:
𝐴̂1 (𝛼𝑓(𝑥) + 𝛽𝑔(𝑥)) = 𝛾𝑥̂(𝛼𝑓(𝑥) + 𝛽𝑔(𝑥)) = 𝛼𝛾𝑥̂𝑓(𝑥) + 𝛽𝛾𝑥̂𝑔(𝑥)
= 𝛼𝐴̂1 𝑓(𝑥) + 𝛽𝐴̂1 𝑔(𝑥)
𝑑
II. 𝐴̂2 = 𝑝̂ = −𝑖ℏ 𝑑𝑥
Linear:
𝑑
𝐴̂2 (𝛼𝑓(𝑥) + 𝛽𝑔(𝑥)) = −𝑖ℏ (𝛼𝑓(𝑥) + 𝛽𝑔(𝑥))
𝑑𝑥
𝑑 𝑑
= −𝛼𝑖ℏ 𝑓(𝑥) − 𝛽𝑖ℏ 𝑔(𝑥) = 𝛼𝐴̂2 𝑓(𝑥) + 𝛽𝐴̂2 𝑔(𝑥)
𝑑𝑥 𝑑𝑥
𝑑
III. 𝐴̂3 = 𝑑𝑥 𝑥̂
𝑑 𝑑
Linear: 𝐴̂3 (𝛼𝑓(𝑥) + 𝛽𝑔(𝑥)) = 𝑑𝑥 [𝑥(𝛼𝑓(𝑥) + 𝛽𝑔(𝑥))] = 𝑑𝑥 𝑥(𝛼𝑓(𝑥) +
𝑑 𝑑
𝛽𝑔(𝑥)) + 𝑥 (𝛼𝑓(𝑥) + 𝛽𝑔(𝑥)) = 𝛼 (𝑓(𝑥) + 𝑥 𝑓(𝑥)) + 𝛽 (𝑔(𝑥) +
𝑑𝑥 𝑑𝑥
𝑑
𝑥 𝑑𝑥 𝑔(𝑥)) = 𝛼𝐴̂3 𝑓(𝑥) + 𝛽𝐴̂3 𝑔(𝑥)
IV. 𝐴̂4 𝑓(𝑥) = 𝑓 2 (𝑥)
Non-linear:
2
𝐴̂4 (𝛼𝑓(𝑥) + 𝛽𝑔(𝑥)) = (𝛼𝑓(𝑥) + 𝛽𝑔(𝑥))
= 𝛼 2 𝑓 2 (𝑥) + 2𝛼𝛽𝑔(𝑥)𝛼𝑓(𝑥) + 𝛽 2 𝑔2 (𝑥)
≠ 𝛼𝐴̂2 𝑓(𝑥) + 𝛽𝐴̂2 𝑔(𝑥)
Since this is true for any differentiable 𝑓(𝑥) it follows that: [𝑝̂ , 𝑥̂] = −𝑖ℏ
𝑑
II. Calculate [cos 𝑥 , ]
𝑑𝑥
𝑑 𝑑 𝑑
[cos 𝑥, ] 𝑓(𝑥) = cos 𝑥 ⋅ 𝑓(𝑥) − (cos 𝑥 ⋅ 𝑓(𝑥))
𝑑𝑥 𝑑𝑥 𝑑𝑥
𝑑𝑓(𝑥) 𝑑𝑓(𝑥)
= cos 𝑥 ⋅ + sin 𝑥 ⋅ 𝑓(𝑥) − cos 𝑥 ⋅ = sin 𝑥 ⋅ 𝑓(𝑥)
𝑑𝑥 𝑑𝑥
𝑑
It follows that: [cos 𝑥, ] = sin 𝑥
𝑑𝑥
1
III. Calculate [𝑝𝑥 , 𝑥]
1 𝑑 1 𝑑 1 1 𝑑𝑓(𝑥)
[𝑝𝑥 , ] 𝑓(𝑥) = −𝑖ℏ [ , ] 𝑓(𝑥) = −𝑖ℏ ( ( ⋅ 𝑓(𝑥)) − ⋅ )
𝑥 𝑑𝑥 𝑥 𝑑𝑥 𝑥 𝑥 𝑑𝑥
1 1 𝑑𝑓(𝑥) 1 𝑑𝑓(𝑥) 1
= −𝑖ℏ (− 2 𝑓(𝑥) + − ) = 𝑖ℏ 2 𝑓(𝑥)
𝑥 𝑥 𝑑𝑥 𝑥 𝑑𝑥 𝑥
a. If 𝐴̂𝑓(𝑥) = 𝛼𝑓(𝑥)
I. Is 𝛽𝑓(𝑥) an eigenfunction of 𝐴̂? What is its eigenvalue?
Yes:
𝐴̂(𝛽𝑓(𝑥)) = 𝛽 (𝐴̂𝑓(𝑥)) = 𝛽(𝛼𝑓(𝑥)) = 𝛼(𝛽𝑓(𝑥))
Eigenvalue: 𝛼
II. Can you find an eigenfunction for 𝛾𝐴̂? What is its eigenvalue?
Yes, take 𝐵̂ = 𝛾𝐴̂
𝐵̂𝑓(𝑥) = 𝛾𝐴̂𝑓(𝑥) = 𝛾𝛼𝑓(𝑥)
Eigenvalue: 𝛾𝛼
4. Hermitian operators:
Postulate 2: Every observable A is represented by a linear, Hermitian
̂ , the measurable values are real – they are the eigenvalues of the
operator 𝑨
operator!
Mathematical exercises:
a) Prove that all eigenvalues of a Hermitian operator are real
∗
For a Hermitian operator ∫ 𝜓𝑛∗ 𝐴̂𝜓𝑛 𝑑𝑥 = ∫(𝐴̂𝜓𝑛 ) 𝜓𝑛 𝑑𝑥
Applying the eigenvalue equation 𝐴̂𝜓𝑛 = 𝑎𝜓𝑛
∫ 𝜓𝑛∗ 𝑎𝜓𝑛 𝑑𝑥 = ∫ (𝑎𝜓𝑛 )∗ 𝜓𝑛 𝑑𝑥
𝑎∫ 𝜓𝑛∗ 𝜓𝑛 𝑑𝑥 = ∫ 𝑎∗ 𝜓𝑛∗ 𝜓𝑛 𝑑𝑥
𝑎∫ 𝜓𝑛∗ 𝜓𝑛 𝑑𝑥 = 𝑎∗ ∫ 𝜓𝑛∗ 𝜓𝑛 𝑑𝑥
𝑎 = 𝑎∗
a is real !!
∗
We demand: ∫ 𝜙 ∗ (𝛼𝑂̂𝜓)𝑑𝑥 = [∫ 𝜓 ∗ (𝛼𝑂̂𝜙)𝑑𝑥 ]
The r.h.s ∫ 𝜙 ∗ (𝛼𝑂̂𝜓)𝑑𝑥 = 𝛼∫ 𝜙 ∗ (𝑂̂𝜓)𝑑𝑥
∗ ∗
The l.h.s : [∫ 𝜓∗ (𝛼𝑂̂𝜙)𝑑𝑥] = 𝛼 ∗ [∫ 𝜓 ∗ (𝑂̂𝜙)𝑑𝑥 ]
Since is real 𝛼 = 𝛼 ∗ and 𝑂̂ is Hermitian
∗
∫ 𝜙 ∗ (𝑂̂𝜓)𝑑𝑥 = [∫ 𝜓 ∗ (𝑂̂𝜙)𝑑𝑥 ]
this is satisfied:
∗
𝛼∫ 𝜙 ∗ (𝑂̂𝜓)𝑑𝑥 = 𝛼 ∗ [∫ 𝜓∗ (𝑂̂𝜙)𝑑𝑥 ]
III. ̂ and 𝑩
𝑨 ̂ are Hermitian. Prove that 𝑨
̂+𝑩̂ is Hermitian
∗
We demand: ∫ 𝜙 ∗ ((𝐴̂ + 𝐵̂)𝜓) 𝑑𝑥 = [∫ 𝜓 ∗ ((𝐴̂ + 𝐵̂)𝜙) 𝑑𝑥 ]
The sum can be separated:
∗ ∗
∫ 𝜙 ∗ (𝐴̂𝜓)𝑑𝑥 + ∫ 𝜙 ∗ (𝐵̂𝜓)𝑑𝑥 = [∫ 𝜓∗ (𝐴̂𝜙)𝑑𝑥 ] +[∫ 𝜓 ∗ (𝐵̂𝜙)𝑑𝑥 ]
which is correct because 𝐴̂ and 𝐵̂ are Hermitian.
IV. Prove that two eigenfunctions with distinct eigenvalues are orthogonal.
If Hermitian:
∗
∫ 𝜓1∗ 𝑂̂𝜓2 𝑑𝑥 = ∫ (𝑂̂ 𝜓1 ) 𝜓2 𝑑𝑥
So:
𝑝̂ 2 ℏ2 𝑑2 ℏ2 𝑑2 2 𝑛𝜋𝑥
𝑇̂𝜓(𝑥) = 𝜓(𝑥) = − 2
𝜓(𝑥) = − 2
(√ sin ( ))
2𝑚 2𝑚 𝑑𝑥 2𝑚 𝑑𝑥 𝑎 𝑎
ℏ2 𝑛𝜋 𝑑 2 𝑛𝜋𝑥
=− ( ) (√ cos ( ))
2𝑚 𝑎 𝑑𝑥 𝑎 𝑎
ℏ2 𝑛𝜋 2 2 𝑛𝜋𝑥
= ( ) (√ sin ( ))
2𝑚 𝑎 𝑎 𝑎
ℏ2 𝑛𝜋 2
Therefore we can only measure 𝑇 = 2𝑚 ( 𝑎 )
𝑖𝑛𝜋𝑥 𝑖𝑛𝜋𝑥
2 𝑛𝜋𝑥 2 𝑒 𝑎 − 𝑒− 𝑎
𝜓(𝑥) = √ sin ( )=√ ( )
𝑎 𝑎 𝑎 2𝑖
𝑒 𝑖𝑘𝑥 is an eigenfunction of 𝑝̂ with ℏ𝑘 as an eigenvalue:
𝑑
−𝑖ℏ 𝑑𝑥 𝑒 𝑖𝑘𝑥 = ℏ𝑘 𝑒 𝑖𝑘𝑥 .
We expanded 𝜓(𝑥) as a sum of eigenfunctions of 𝑝̂ , now it is
𝑛𝜋
clear that the possible measurements are 𝑝 = ℏ 𝑎 and
𝑛𝜋
𝑝 = −ℏ 𝑎
6. Important Integrals:
∞
a. 𝐼 = ∫−∞ exp(−𝛼𝑥 2 ) 𝑑𝑥
𝜋
And 𝐼 = √
𝛼
∞
b. 𝐼2 = ∫−∞ exp(−𝛼𝑥 2 + 𝛽𝑥 + 𝛾) 𝑑𝑥
Use:
−𝛼𝑥 2 + 𝛽𝑥 + 𝛾 = −𝑎(𝑥 + 𝑏)2 + 𝑐
∞
d. 𝐼4 = ∫0 xexp(−𝛼𝑥 2 ) 𝑑𝑥
here we just need to use the indefinite integral to get
exp(−𝛼02 ) 1
𝐼4 = 0 − (− )=
2𝛼 2𝛼
∞ 2 2)
e. 𝐼5 = ∫−∞ x exp(−𝛼𝑥 𝑑𝑥
𝜕
Use: xexp(−𝛼𝑥 2 ) = − (exp(−𝛼𝑥 2 ))
𝜕𝛼
∞ 𝜕
Here we notice that 𝐼5 = ∫−∞ − 𝜕𝛼 (exp(−𝛼𝑥 2 ))𝑑𝑥
We are allowed to interchange the order of derivative and integral:
𝜕 ∞ 𝜕 1 √𝜋 √𝜋
− 𝜕𝛼 (∫−∞ exp(−𝛼𝑥 2 ) 𝑑𝑥 ) = − 𝜕𝛼 𝐼 = − (− 2 3 ) = 2𝛼
𝛼2 √𝛼