BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture - 06, 21 January 2025, Tuesday

Instructor: Dr. Satyajit Patra

Topics Covered in the Last Lecture

• Operators and Observables

• Postulates of Quantum Mechanics

• Applications of QM to Microscopic Systems

1. Particle confined in a 1-D, 2-D, and 3-D box

2. Vibrational motion: Simple Harmonic Oscillator
3. Particle on a ring

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Objective of Today’s Lecture

• Applications of QM to Microscopic Systems

4. Particle on a sphere (3-D rigid Rotor)

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General Chemistry-summary & problems
Vibrational motion
• Classical and quantum pictures; Hamiltonian operator (both kinetic
and potential energies); wave function (3 parts – normalization
constant, Hermite polynomial, exponential factor); energies En = (n +
½) hν ; zero-point energy hν/2; even spacing; Large n values –
classical picture – correspondence principle.
Motion on a circular path
• No potential energy; angular momentum; Hamiltonian operator polar
coordinates only one variable; cyclic boundary conditions → mλ =
1
2πr; normalized wavefunction 𝑒 𝑖𝑚𝜙 ; energy = m2ℏ2/2I; m = 0,
2𝜋
  ….; degeneracy; no zero point energy; angular momentum
= mlℏ (quantized).

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General Chemistry-summary & problems
Translational motion in 1-dimension: particle in a box
෡ = 𝐸𝜓
𝐻𝜓 ℏ2 𝑑 2
෡=−
𝐻
𝑑2 𝜓 2𝑚𝐸 2𝑚 𝑑𝑥 2
S.E. + 𝜓 = 0 and boundary condition
𝑑𝑥 2 ℏ 2
2 𝑛𝜋𝑥
Solution 𝜓= sin ;n = 1,2,3, …
𝐿 𝐿
Determine 𝐸 2 , 𝐸 2 , 𝐸 2 , 𝑝𝑥2 , 𝑝𝑥 2 , 𝑥 2 , 𝑥 2 for the ground state (n = 1)

Do not you think 𝐸 2 , 𝐸 2 and 𝐸 2

are the same?

Yes, they will be the same.

What is about
𝑝𝑥2 , 𝑝𝑥 2 and 𝑥 2 , 𝑥 2 ?

Key: check wavefunction is the eigenfunction of the operator

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General Chemistry-summary & problems
Quantum Mechanics to vibrational motion
ℏ2 𝑑 2 1 2
෡ = 𝐸𝜓
𝐻𝜓 ෡=−
𝐻 2
+ 𝑘𝑥
2𝑚 𝑑𝑥 2
𝑑2 𝜓 2𝑚 1
S.E. + (𝐸 − 𝑘𝑥 2 )𝜓 = 0 and boundary conditions
𝑑𝑥 2 ℏ 2 2
𝑛 −𝛼𝑥 2 /2
Solution 𝜓 = 𝑁𝑛 𝐻 𝑒 ; n = 0,1,2,3, …

Determine 𝐸 2 , 𝐸 2 , 𝑝𝑥2 , 𝑝𝑥 2 , 𝑥 2 , 𝑥 2
for the ground state (n = 0)

Quantum mechanics to particle moving on a circular path

෡ = 𝐸𝜓
𝐻𝜓 ℏ2 𝑑 2
෡=−
𝐻
𝑑2 𝜓 2𝐼𝐸 2𝐼 𝑑𝜙 2
S.E. + 𝜓 = 0 and boundary conditions
𝑑 𝜙2 ℏ2
𝑒 𝑖𝑚𝜙
Solution 𝜓 = 2𝜋
, 𝑚 = 0, ±1, ±2, ±3, … ,
Determine 𝐸, 𝐿𝑧
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Particle on a sphere

Example 4: Application of Quantum Mechanics to

Particle on a Sphere (3-D Rigid Rotor)
z

r y

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Rotation in three dimensions
• Consider a particle moving on the surface of a sphere.
• Understanding this rotational motion in three dimensions will help
us understand the motion of electrons around nuclei in atoms.
• Study of molecular rotations gives us bond lengths etc.
𝑉=0
• Two angles (particle confined to a spherical space)
𝜙 - the azimuthal angle z
𝜃 - the colatitude
𝜓(𝑥, 𝑦, 𝑧) ⟶ 𝜓(𝜃, 𝜙)
r y
• Motion of a particle over sphere is like motion of
particle over a stack of rings, with additional x
freedom to migrate between rings.
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Spherical polar → Cartesian
Image result for spherical polar coordinates

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Hamiltonian operator in polar coordinates

−  2
Hˆ =  2 + Vˆ
2m

  2
 2
 2


 = 2 +
2
+ 2  …….. Cartesian coordinates
x y z 
2

  2
2  1  1  2
1     
 = 2 +
2
+ 2 2 + 
 sin   
 

r     2
       
 r r r  sin sin
…… polar coordinates
Since r is fixed
1  1 2 1     
 = 2
2
 2 +  sin  
r    
 sin    sin    
2

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The Schrödinger equation: particle on a sphere
1  1 2 1     
 = 2
2
 2 +  sin  
r    
 sin    sin     r constant
2

V=0
Laplacian Legendrian
Operator Operator 2
 1 2 −  2
 = 2  
2
Hˆ =  2 + Vˆ
r  2m
෡ 𝜃, 𝜙 = 𝐸𝜓 𝜃, 𝜙
The Schrödinger equation: 𝐻𝜓
Since,
2
2𝐼𝐸 𝐼 = 𝑚𝑟 2
Λ 𝜓 𝜃, 𝜙 = − 2 𝜓 𝜃, 𝜙
Using 𝜓 𝜃, 𝜙 = Θ(𝜃)Φ(𝜙)
ℏ
Separation of variables technique 2
2𝐼𝐸
Λ Θ(𝜃)Φ(𝜙) = − 2 Θ(𝜃)Φ(𝜙)
ℏ
Solving the SE and applying the appropriate cyclic boundary conditions
(more details see the slide no. 16,17)
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Particle on a sphere rigid rotor: boundary
conditions
• Two variables : Polar angle – colatitude 𝜃 & Azimuthal angle 𝜙
• The problem can be visualized as a set of “particle in a ring” problems with
the addition of movement between rings.

• Imposing first boundary condition: The acceptable wavefunction must

describe the motion of the particle round the equator or any parallel ring.
That means 𝜙 = 0 to 2𝜋 and this brings in the quantum number, 𝑚𝑙
The angle 𝜙 represents the angle about the equator; 𝟎 ≤ 𝜙 ≤ 𝟐𝝅 (similar to
particle in a ring).
• Imposing second boundary condition: The acceptable wavefunction must
describe the motion of the particle across the poles. That means 𝜃 = 0 to 𝜋;
and this constraint introduces a second quantum number 𝑙 called orbital
momentum quantum number.
The angle 𝜃 represents the declination from the north pole; 𝟎 ≤ 𝜃 ≤ 𝝅
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Particle on a sphere - rigid rotor:
acceptable solution of wavefunction
•The acceptable solutions for the wavefunctions
𝑚𝑙 𝑒 𝑖𝑚𝑙 𝜙
𝜓𝑙,𝑚𝑙 𝜃, 𝜙 = 𝑁𝑙𝑚𝑙 𝑃𝑙 cos 𝜃 ∙ 1/2
2𝜋
Normalized Θ(𝜃) Normalized Φ(𝜙)

such that 𝑙 = 0,1,2, …

For a given value of 𝑙 there are 2𝑙 + 1 permitted values of the magnetic
quantum no. 𝑚𝑙 . (𝑚𝑙 = 𝑙, 𝑙 − 1, … , −𝑙)

Each set of quantum numbers (𝑙, 𝑚𝑙 ) represent a unique state.

•The acceptable solutions for the wavefunctions are known as spherical

harmonics, and denoted as 𝑌𝑙,𝑚𝑙 𝜃, 𝜙 ≡ 𝜓𝑙,𝑚𝑙 𝜃, 𝜙

• Rigid = fixed r; molecular rotations – fixed bond length;

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Particle on a sphere rigid rotor:
energy & momentum
• The solution of Schrodinger eq. also gives the energy, 𝐸 of the particle
restricted to the values:
𝑙(𝑙+1) 2
𝐸= ℏ , 𝑙 = 0,1,2,3, … Energy is quantized and is independent of 𝑚
2𝐼
(more details see the slide no. 18)

• A level with quantum no. 𝑙 is (2𝑙 + 1) fold degenerate; Degeneracy =

(2𝑙 + 1)
• Total angular momentum is quantized and 𝐿 = 𝑙(𝑙 + 1) 1/2 ℏ

(more details see the slide no. 18)

• z-component of the angular momentum, 𝐿𝑧 = 𝑚𝑙 ℏ

(𝐿𝑥 and 𝐿𝑦 are now not precisely known)

for a given 𝑙, 𝑚𝑙 may take on one of the 2𝑙 + 1 values (−𝑙, -(𝑙 + 1), ...0, ...,
(𝑙 − 1), 𝑙)
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Space quantization- 𝐿𝑧
Two aspects of the quantization of
angular momentum vector (𝐿), are the
magnitude and its orientation.

For each 𝑙 , there could be limited 𝑚𝑙

values,
the orientation of a rotating body is
quantized.

For a particle having a certain energy

(e.g. characterized by 𝑙 = 2), the plane of
rotation can only take a discrete range of
orientations (characterized by one of the
2𝑙 + 1 values of 𝑚𝑙 )
Space quantization
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Vector model of angular momentum

Case 𝑙 = 2, 𝑚𝑙 = 2,1,0, −1, −2

𝐿𝑧 𝐿

𝐿 is a vector (Lx and Ly are not precisely known).

𝐿 lies on the surface of a cone.
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Approach to solve Schrödinger equation:
particle on a sphere
2𝐼𝐸 2
The Schrödinger equation: Λ 𝜓 𝜃, 𝜙 = − 2 𝐸𝜓 𝜃, 𝜙
ℏ
1 𝜕2 1 𝜕 𝜕
Using Λ2 = + sin 𝜃 and 𝜓 𝜃, 𝜙 = Θ(𝜃)Φ(𝜙)
sin2 𝜃 𝜕𝜙2 sin 𝜃 𝜕𝜃 𝜕𝜃

1 𝜕 2 ΘΦ 1 𝜕 𝜕 ΘΦ 2𝐼𝐸
+ sin 𝜃 = −𝛽 ΘΦ where 𝛽 = ℏ2
sin2 𝜃 𝜕𝜙 2 sin 𝜃 𝜕𝜃 𝜕𝜃

1 𝑑2 Φ sin 𝜃 𝑑 𝑑Θ
+ sin 𝜃 + 𝛽 sin2 𝜃=0
Φ 𝜕𝜙2 Θ 𝑑𝜃 𝜕𝜃

1 𝑑2 Φ sin 𝜃 𝑑 𝑑Θ
= −𝑚𝑙2 ; sin 𝜃 + 𝛽 sin2 𝜃= 𝑚𝑙2
Φ 𝜕𝜙2 Θ 𝑑𝜃 𝜕𝜃

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Approach to solve Schrödinger equation:
particle on a sphere
sin 𝜃 𝑑 𝑑Θ
1𝑑 Φ2
2
sin 𝜃 + 𝛽 sin2 𝜃= 𝑚𝑙2
= −𝑚 Θ 𝑑𝜃 𝜕𝜃
𝑙
Φ 𝜕𝜙 2
and boundary condition
and boundary condition
Solution:
Solution: 𝑚𝑙 𝑑 𝑚𝑙
𝑚𝑙 2
𝑒 𝑖𝑚𝑙 𝜙 𝑃𝑙 𝑥 = 1− 𝑥 2 𝑚
𝑃𝑙 (𝑥)
Φ𝑚𝑙 𝜙 = 𝑑𝑥 𝑙
2𝜋 where 𝑥 = cos 𝜃 and Θ 𝜃 = 𝑃(𝑥)
𝑚𝑙 = 0, ±1, ±2, … • It is found that 𝛽 = 𝑙(𝑙 + 1), where
𝑙 = 0,1,2, …
𝑚𝑙 = 0, ±1, ±2, … , ±𝑙
𝑚𝑙
• Normalization constant of 𝑃𝑙 𝑥
1/2
2𝑙 + 1 𝑙 − 𝑚𝑙 !
𝑁𝑙𝑚𝑙 =
2 𝑙 + 𝑚𝑙 !
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Particle on a sphere: Wavefunction

𝑥 = cos 𝜃 and Θ = 𝑃(𝑥) we have

𝛽 = 𝑙(𝑙 + 1)

𝑑2 𝑃 𝑑𝑃 𝑚2
⟹ 1 − 𝑥2 − 2𝑥 + 𝑙 𝑙+1 − 𝑃 𝑥 =0
𝑑𝑥 2 𝑑𝑥 1 − 𝑥2

Solution of this equation is

𝑚𝑙
𝑚𝑙 𝑑 𝑚𝑙
𝑃𝑙 𝑥 = 1− 𝑥2 2 𝑚
𝑃𝑙 (𝑥)
𝑑𝑥 𝑙

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Particle on a sphere: Wavefunction

𝑌𝑙,𝑚𝑙 𝜃, 𝜙 = Θ 𝜃 Φ 𝜙
⟹ Spherical Harmonics
𝑚𝑙
𝑌𝑙,𝑚𝑙 𝜃, 𝜙 = 𝑁𝑙,𝑚𝑙 𝑃𝑙 cos 𝜃 𝑒 𝑖𝑚𝜙

2𝑙 + 1 𝑙 − 𝑚𝑙 ! 𝑚𝑙
𝑌𝑙,𝑚𝑙 𝜃, 𝜙 = 𝑃𝑙 cos 𝜃 𝑒 𝑖𝑚𝜙
4𝜋 𝑙 + 𝑚𝑙 !

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Particle on a sphere rigid rotor:
energy & momentum
Square of the angular momentum operator
1 𝜕2 1 𝜕 𝜕
𝐿෠2 = −ℏ2 2 2 + sin 𝜃
sin 𝜃 𝜕𝜙 sin 𝜃 𝜕𝜃 𝜕𝜃
We learnt
1 𝜕2 1 𝜕 𝜕
+ sin 𝜃 𝑌 𝜃, 𝜙 = −𝛽𝑌 𝜃, 𝜙
sin2 𝜃 𝜕𝜙 2 sin 𝜃 𝜕𝜃 𝜕𝜃
Multiplying both side by −ℏ2 𝛽 = 𝑙(𝑙 + 1)

1 𝜕2 1 𝜕 𝜕
−ℏ2 + sin 𝜃 𝑌 𝜃, 𝜙 = ℏ2 𝑙 𝑙 + 1 𝑌 𝜃, 𝜙
sin2 𝜃 𝜕𝜙 2 sin 𝜃 𝜕𝜃 𝜕𝜃

𝐿෠2 𝑌 𝜃, 𝜙 = ℏ2 𝑙 𝑙 + 1 𝑌 𝜃, 𝜙
Energy:
𝐿෠2 ℏ2 𝑙(𝑙 + 1)
෡ 𝜃, 𝜙 = 𝑌 𝜃, 𝜙 =
𝐻𝑌 𝑌 𝜃, 𝜙
2𝐼 2𝐼
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Particle on a sphere rigid rotor:
energy & momentum
• The solution of Schrodinger eq. also gives the energy, 𝐸 of the
particle restricted to the values:
𝑙(𝑙+1) 2 Energy is quantized
𝐸= ℏ , 𝑙 = 0,1,2,3, …
2𝐼 and is independent of 𝑚𝑙
(more details see the slide no. 18)
• A level with quantum no. 𝑙 is (2𝑙 + 1) fold degenerate; Degeneracy
= (2𝑙 + 1)
1/2
• Total angular momentum is quantized and 𝐿 = 𝑙(𝑙 + 1) ℏ
(more details see the slide no. 18)
• z-component of the angular momentum, 𝐿𝑧 = 𝑚𝑙 ℏ

(𝐿𝑥 and 𝐿𝑦 are now not precisely known)

for a given 𝑙, 𝑚𝑙 may take on one of the 2𝑙 + 1 values (−𝑙, -(𝑙 + 1),
...0, ..., (𝑙 − 1), 𝑙)

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