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CHEM F111 General Chemistry Lecture 05

Particle on ring, rigid rotor, harmonic oscillator
 Review of lecture 04

• Particle in 1D box
• Boundary conditions
• Salient features of the wavefunctions and energy levels

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PIB wavefunctions (revision)

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Characteristics of PIB wavefunctions
(revision)
Wavelength in a given state equals to 2L/n.

The number of nodes in the wavefunction equals to n-1.

The ground state wavefunction does not have nodes.
Energy increases with increase in the number of nodes. (Why?)

The wavefunctions are alternately symmetric and antisymmetric about the

midpoint of the box.
2 nπx
√
ψ n ( x)=
L
sin( )L
; n=1,2,3 ,…

Non-zero energy for the ground state: E1 = h2/8mL2,

Note the dependence of the energy on m and L. As they increase, the separation
between the energy levels decreases.

As the quantum number, n tends to infinity, the probability distribution becomes

uniform over the entire length of the box.
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PIB – 2D
2D or rectangular box: [V(x,y)=0 for 0 ≤x≤a ; 0 ≤y≤b and V(x,y)=∞ otherwise]
Schrödinger equation for particle in a 2D box:
2 2
ℏ2 ∂ ψ ∂ ψ
−
(
2m ∂x ∂ y2
+ 2) =E ψ

The motions along the two directions being independent of each other, the
wavefunction must be expressible as ψ( x , y )=ψ x ( x) ψ y ( y)
Let E = Ex + Ey. Then, one can solve to get:
ℏ2 d2 ψx d2 ψ y
−
2m (
ψy
dx 2
+ψx
dy 2 )
=( E x +E y ) ψx ψ y

2 2
2
1 d ψ 1 d ψy
−
ℏ
ψ (
2m x d x 2
x
+ ψ y d y
2 )
=( E x + E y )

Rearranging, we have:
2 2
ℏ 2 1 d ψx ℏ2 1 d ψ y
− −E x = +E y
2 m ψ x d x2 2 m ψ y d y2

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PIB – 2D
2D or rectangular box: [V(x,y)=0 for 0 ≤x≤a ; 0 ≤y≤b and V(x,y)=∞ otherwise]
We have obtained: ℏ 2 1 d 2 ψx 2
ℏ 1 d 2
ψy
− ψ 2
−E x = ψ 2
+E y
2m x d x 2m y d y
The LHS is a function of x alone and RHS is a function of y alone, and x and y are
independent variables. Therefore, each side would be equal to a constant. Since Ex
and Ey are unknown constants, their values may be tuned such that each side in the
above equation equals
2
to zero, and we have:
ℏ 1 d ψx
2
d 2 ψ x 2 mE x
− −E x =0 ⇒ + 2 ψ x =0 ;0≤x≤a
2 m ψ x d x2 dx 2
ℏ
2
ℏ2 1 d ψ y d 2 ψ y 2 mE y
+ E y =0 ⇒ + 2 ψ y =0 ; 0≤ y≤b
2 m ψ y d y2 dy 2
ℏ
Thus, we obtain two 1D equations which can be solved by applying the boundary
conditions to get:
2 nx π x ny π y h 2
n2x n2y
ψn , n ( x , y)=ψx , n ( x) ψ y , n ( y )=
x y x y (
√ ab
sin) (a
sin ) b
En ,n =
x y (+
8 m a2 b2 )
n x =1,2,3 ,…; n y =1,2,3 ,…
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PIB – 3D
3D box: [V(x,y,z)=0 for 0 ≤x≤a ; 0 ≤y≤b;
≤y≤b 0 ≤z≤c and V(x,y,z)=∞ otherwise]
The logic can be extended to 3D box or even multidimensional case.
2 2 2 2 2
For 3D, the kinetic energy operator is given by − ℏ ℏ
∂ + ∂
(
+ ∂
2 m ∂ x2 ∂ y2 ∂ z 2
≡−
2m
∇
2
)
The normalized wavefunction and energy are:
8 nx π x ny π y nz π z
ψn , n
x y z
√
, n ( x , y , z)=
abc (
sin
a ) (sin
b ) ( )
sin
nx =1,2,3 ,…; n y =1,2,3 ,…; n z =1,2,3 ,…
c En ,n
x y ,n
z
=
h2
n 2

(
x
+
n 2
y
8 m a2 b2 c 2
+
n 2
z
)
Special cases:
Square box (2D box with both the sides equal)
Cubic box (3D box with both the sides equal)
Cuboid box (3D box with two sides equal)

Energetic degeneracy – two or more energy levels having same energy

Homework – For Square and cubic boxes, find the energies of first ten levels and
the degeneracy of each level.
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Rotation: particle on a ring

Particle constrained to move on a ring of radius r. Take the potential

energy to be zero as long as particle on the ring, infinite otherwise

V(r=r0)=0; V(r≠r0)=∞.
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 Rotation: particle on a ring

Angular momentum: |⃗J|=|⃗r ×⃗p|= I ω

I =μ r 2 (Moment of intertia of the particle of mass μ moving in an orbit of radius r)

Consider the rotation in a plane orbit, say, in xy-plane, and centered at origin.
The angular momentum vector would lie along the z-axis.

In polar coordinates, the operator form for z-component of the angular

momentum is given by
ℏ d
J^ z = ; with x=r cos ϕ ; y=r sin ϕ
i dϕ
J 2z
The kinetic energy corresponding to the rotational motion is
2I
J^ 2z ℏ 2
d 2
The rotational kinetic energy operator would, thus, be =−
2I 2 I d ϕ2
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 Rotation: particle on a ring

We have V(r)=0 at r=r0 and infinite otherwise.

Thus, for the orbit of fixed radius, r=r0, the Schrödinger equation takes the form:
2
ℏ 2 d Φ (ϕ)
− = E Φ(ϕ)
2 I d ϕ2

The wavefunction, Φ (ϕ) for rotation about the z-axis is a pure function of the
azimuthal angle, ϕ .

The single-valuedness of the wavefunction requires that its values should repeat
after each rotation, which results in the periodic boundary condition (also
referred to as cyclic boundary condition):
Φ (2 π+ϕ)=Φ (ϕ)

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Particle on ring: Boundary condition

Cyclic boundary condition (single valued):

nλ = 2πr; n = 0, ±1,±2,±3,….

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 Particle on a ring

ℏ 2
d 2 Φ (ϕ) d 2 Φ (ϕ) 2 IE
We have − = E Φ(ϕ) + 2 Φ (ϕ)=0
2 I d ϕ2 dϕ
2
ℏ
2
2 IE 2 d Φ (ϕ) 2
We substitute 2 =m and get 2
+m Φ(ϕ)=0
ℏ dϕ

im ϕ
The general solution is of the form Φ (ϕ)= Ae

Now we apply the periodic boundary condition and solve:

Φ (2 π+ϕ)= Ae i m(2 π+ ϕ )=Φ (ϕ)= Ae im ϕ
Ae 2 π m i e im ϕ = Ae i m ϕ
e 2 π m i=1 ⇒ m=0,±1,±2,±3,…

Homework: Normalize the wavefunction to evaluate the constant, A.

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Energy Levels

Energy: m2 ℏ2 m2 h2 m2 ℏ2 m2 h2
E m= = 2 = 2
= 2 2
2I 8 π I 2 μ r0 8 π μ r0

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 Particle on a ring: Characteristic
features
Degeneracy of energy levels: All levels except for m=0, are doubly
degenerate, i.e. there are two distinct states of the same energy. The two differ
in the sense of the rotation
Angular momentum ȷz is quantized, ȷz = mħ
No zero point energy

What is the form of the wavefunction corresponding to m=0? Discuss the

consequences (Homework)
Compare the particle on a ring with 1D-PIB. What are the similarities and the
differences?

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Particle moving on the surface of a
sphere (Rigid Rotor)
Polar and azimuthal angles:
Boundary conditions:
Φ (2 π+ϕ)=Φ (ϕ)
Θ(π+θ)=Θ(π−θ)

Hamiltonian eigenfunctions of rigid rotor are also the

eigenfunctions of the angular momentum squared
operator and are called spherical harmonics.
Y (θ , ϕ)=Θ(θ) Φ(ϕ)

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Rotation on a sphere –
rigid rotor
Particle constrained to rotate on surface of sphere of radius R
Classically, E = J2/2mR2
Schrödinger equation involves the polar angle θ and the azimuthal
angle φ as variables
On solving, and imposing the appropriate boundary conditions,
obtain the ‘spherical harmonics,’ Yl,m (θ,φ), characterized by two
l

quantum numbers l and ml.

The spherical harmonics are a product of two functions
Yl,m (θ,φ) = Θl,m (θ)Φm (φ); ml = -l, -l+1,..0,..l-1, l
l l l

Energy El = l(l + 1)ħ2/2I ← Depends on l, not on ml

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Rigid Rotor – angular momentum

Quantum number l allowed to take on values 0,1,2,…

Magnitude of the orbital angular momentum is |J| = [l(l+1)]1/2ħ
For a given value of l, the quantum number ml can take any of the 2l+1
values -l,-(l+1),…,0,…,l–1,l. Degeneracy =2l +1

The value of the z-component of the angular momentum is mlħ.

Two aspects of the quantization of angular momentum, namely, the

magnitude of the angular momentum, and the orientation of the angular
momentum vector relative to z-axis.

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Case l = 1, ml = 1, 0, -1

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Case l = 2, ml = 2, 1, 0, -1, -2

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 1D simple harmonic motion

Hooke’s law: Restoring force = -kx ( k is force constant, x is the displacement

from equilibrium)
Potential energy V(x) = ½ kx2
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1D Classical harmonic oscillator

• Total energy of a classical harmonic oscillator in a given state remains constant.

• The kinetic energy is maximum at the mean position and zero at the turning
points
• The potential energy is zero at the mean position and maximum at the turning
points
• The oscillator can be excited to a state of any arbitrary value of the total energy

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 1D Quantum harmonic oscillator

Schrödinger equation for 1-D harmonic oscillator is given by:

2
ℏ 2 d ψ( x) 1 2
− + kx ψ( x)=E ψ ( x) (Eq 1)
2 m dx 2 2

Boundary conditions? ψ(∞)=0=ψ(−∞)

d 2 ψ( x) (2 mE−mkx 2 ) (Eq 2)
We rearrange Eq 1 to get: 2
+ 2
ψ( x)=0
dx ℏ

Now, we make substitutions: k/m=ω2; λ=2E/(ħω);

λ=2E/(ħω) α=mω/ħ;
α=mω/ħ y=α½x ; solve and
simply to get

d 2 ψ( y) 2
(Eq 3)
2
+(λ− y ) ψ( y )=0
dy

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 1D harmonic oscillator

d 2 ψ( y) 2
(Eq 3)
2
+(λ− y ) ψ( y )=0
dy
The solution of this equation is a bit involved and we will not solve it here. The
solutions to the above equation have the form:

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 1D harmonic oscillator

d 2 ψ( y) 2
(Eq 3)
2
+(λ− y ) ψ( y )=0
dy
The solution of this equation is a bit involved and we will not solve it here. The
solutions to the above equation have the form:
− y2 / 2
ψv ( y)=N v H v ( y )e ; v=0,1,2 ,…

where, v is vibrational quantum number, Hv(y)(y is Hermite polynomial in y of

degree v, Nv is normalization constant for the wavefunction of the vth state.
The energy levels are non-degenerate and are given by:

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 1D harmonic oscillator

d 2 ψ( y) 2
(Eq 3)
2
+(λ− y ) ψ( y )=0
dy
The solution of this equation is a bit involved and we will not solve it here. The
solutions to the above equation have the form:
− y2 / 2
ψv ( y)=N v H v ( y )e ; v=0,1,2 ,…

where, v is vibrational quantum number, Hv(y)(y is Hermite polynomial in y of

degree v, Nv is normalization constant for the wavefunction of the vth state.
The energy levels are non-degenerate and are given by:
1
E v =(v + )h υ; v=0,1,2 ,…; υ is fundamental vibrational frequency .
2

1 k
υ=
2π m√
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1D harmonic oscillator

Hermite polynomials can be easily obtained using the following formula:

v − y2
d (e )
v y
2

H v ( y )=(−1) e v
; v=0,1,2 ,…
dy

H 0 ( y )=1
H 1 ( y)=2 y
H 2 ( y)=4 y 2 −2
H 3 ( y )=8 y 3 −12 y
H 4 ( y)=16 y 4 −48 y 2 +12
H 5 ( y)=32 y 5 −160 y 3 +120 y

ψ v ( y)=N v H v ( y )e
− y2 / 2 1
E v =(v + )h υ
2
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1D HO: Wavefunctions and probability
distribution

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1D HO: Wavefunctions and probability
distribution

v=3
v=3

v=2
v=2
v=1
v=1

v=0 v=0

Ψ (not to scale)
Ψ*Ψ
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1D harmonic oscillator: characteristic
features

●
The wavefunctions are alternately even and odd functions corresponding
to the even and odd values of v (vibrational quantum number).
●
Number of nodes = v, no nodes for the ground state
● Ev=(v+½)hυ; Zero point energy E0= ½ hυ
●
For ground state, probability density is maximum at mean position. As v
increases, the probability density max gradually shifts towards the
turning points – classical limit obtained as v→∞

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