Chemistry 120A Problem Set 3

Due Feb, 2024

Problem 1
Solution:
a)
h d d2 i d d2 d2 d d2 d3 d d d2
x2 , x 2 = x2 (x 2 ) − x 2 (x2 ) = x2 2 + x3 3 − x (2x + x2 2 )
dx dx dx dx dx dx dx dx dx dx dx
2 3 2 2 3 2
d d d d d d d d
= x2 2 + x3 3 − x(2 + 2x 2 + 2x 2 + x2 3 ) = −3x2 2 − 2x
dx dx dx dx dx dx dx dx
b)
h d d2 i d d2 d2 d d2 d3 d d d2
x , x3 2 = x (x3 2 ) − x3 2 (x ) = 3x3 2 + x4 3 − x3 ( + x 2 )
dx dx dx dx dx dx dx dx dx dx dx
2 3 2 2 3 2
3 d 4 d 3 d d d 3 d
= 3x +x − x ( 2 + 2 + x 3) = x
dx2 dx3 dx dx dx dx2
c)
h i  ∂  ∂   ∂  ∂ 
px , py = px py − py px = − iℏ − iℏ − − iℏ − iℏ
∂x ∂y ∂y ∂x
 ∂2 ∂ 2 
= −ℏ2 − =0
∂x∂y ∂y∂x
d)
[Lz , Lx ] = iℏLy
h i
xpy − ypx , ypz − zpy = (xpy − ypx )(ypz − zpy ) − (ypz − zpy )(xpy − ypx )
= (xpy ypz − xpy zpy − ypx ypz + ypx zpy ) − (ypz xpy − ypz ypx − zpy xpy + zpy ypx )
= (xpy ypz − ypz xpy ) + (zpy xpy − xpy zpy ) + (ypz ypx − ypx ypz ) + (ypx zpy − zpy ypx )
nh ∂ ∂ ∂ ∂ i h ∂ ∂ ∂ ∂ i
= −ℏ2 x (y ) − y (x ) + z (x ) − x (z )
∂y ∂z ∂z ∂y ∂y ∂y ∂y ∂y
h ∂ ∂ ∂ ∂ i h ∂ ∂ ∂ ∂ io
+ y (y ) − y (y ) + y (z ) − z (y )
∂z ∂x ∂x ∂z ∂x ∂y ∂y ∂x
2 2  2
h ∂ ∂ ∂  ∂ ∂2 
= −ℏ2 x + xy − yx + zx 2 − xz 2
∂z ∂y∂z ∂z∂y ∂y ∂y
2 2  2 2 i
 ∂ ∂  ∂ ∂ ∂
+ y2 − y2 + yz −z − zy
∂z∂x ∂x∂z ∂x∂y ∂x ∂y∂x
 ∂ ∂ 
= −ℏ2 x − z = −iℏ(xpz − zpx ) = iℏ(zpx − xpz )
∂z ∂x
1
Problem 2
Solution:
a)
d d
Z 1 √ 2 ∗ d √ 2 Z 1
1 5
⟨ ⟩ = ⟨ψ| ψ⟩ = ( 5x ) ( 5x )dx = 10 x3 dx = 10 · x4 |10 =
dx dx 0 dx 0 4 2
b) suppose the normalizaiton constant is A, then we have
Z 2 Z 2
3/2 ikx ∗ 3/2 ikx
2
1 = ⟨Aψ|Aψ⟩ = |A| ⟨ψ|ψ⟩ = |A| 2
(x e ) (x e )dx = |A| 2
(x3/2 e−ikx )(x3/2 eikx )dx
0 0
Z 2
1 1 1
= |A|2 x3 dx = |A|2 x4 |20 = 4|A|2 ⇒ |A|2 = ⇒ can choose A =
0 4 4 2
1
ψnormalized = Aψ = x3/2 eikx
2

Problem 3
Solution:
a) From the harmonic oscillator results
s
ω 1 k m1 · m2
ν= = ⇒ k = µ(2πν)2 , µ=
2π 2π µ m1 + m2
1 a.u. · 35 a.u.
⇒k= · (1.66 × 10−27 kg · a.u.−1 ) · (2π · 8.65 × 1013 s−1 )2 ≈ 4.77 × 102 N · m−1
1 a.u. + 35 a.u.
b)
1 1 1 1ν 1 8.65 × 1013 s−1
E0 = hν = hcν̃ ⇒ E0 (cm−1 ) = ν̃ = = · ≈ 1.44 × 103 cm−1
2 2 2 2c 2 2.998 × 1010 cm · s−1
c) suppose the force constants can be viewed as the same, from a) we have
r
1 · 35 2 + 37
r r
ν2 µ1 µ1
= ⇒ ν2 = ν1 = · · 8.65 × 1013 Hz ≈ 6.19 × 1013 Hz
ν1 µ2 µ2 1 + 35 2 · 37
d)
e) view the rotation of diatomic molecules as rigid rotator, we have the energy:
s
ℏ2 J(J + 1) ℏ2 J(J + 1) h h
EJ = = 2
= hcB̃J(J + 1), B̃ = 2 ⇒R=
2I 2µR 8π cµR2 8π 2 cµB̃
s
1 h
⇒ ∆EJ = EJ+1 − EJ = 2hcB̃(J + 1) ⇒ ν̃ = 2B̃(J + 1) ⇒ ∆ν̃ = 2B̃ ⇒ R =
2π cµ∆ν̃
s
1 6.626 × 10−34 J · s
⇒ R= 1·127 ≈ 163 pm
2π (2.998 × 1010 cm · s−1 ) · ( 1+127 · 1.66 × 10−27 kg) · 12.8cm−1

2
Problem 4
Solution:
a) See plot below.

b) There are a few close point (e.g. (0,3), (1, 2), (2,0)), but no actual degeneracies.
c) Eventually, yes. For example, (0, 24) and (96, 0) will both have 4825 cm−1 .
d) From the problem, we have:
1
Ev,J = hcν̃( + v) + hcB̃J(J + 1)
2
⇒ ∆E = Ev=2,J=3 − Ev=1,J=4 = hcν̃ − 8hcB̃
|∆E(cm−1 )| = |ν̃ − 8B̃| = 14 cm−1

Problem 5
Solution:
We simply recognize that we have two degrees of freedom - the z -coordinate and the along
length a , and the angle ϕ around the radius of the cylinder. Similarly to a 2-dimensional
particle in a box, this is just a particle on a ring combined with a 1D particle-in-a-box:
Ψ = ΨPIB (z) Ψring (ϕ). Another way to see why it’s true is to take a sheet of paper

3
to represent a 2D box and make a cylinder out of it - the two degrees of freedom are
preserved, but one of them is now better described by an angle. Thus,
r r
n1 n2 2  n πz  1
1 in2 ϕ 1  n πz 
1
Ψn1 ,n2 = ΨPIB (z) Ψring (ϕ) = sin √ e = sin ein2 ϕ
a a 2π πa a

Of course the energies are just the sum of the two,

h2 n21 ℏ2 n22
En1 n2 = +
8ma2 2mr2