BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 6

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 Summary (Lecture 5)

Applications of Quantum Mechanics to

Microscopic system
Quantum Mechanical Treatment of an Harmonic
Oscillator: Solution of Schrondinger Equation
Eigen Value of Energies
Wavefunctions
Physical Interpretation
Quantum Mechanical Treatment of a Particle in a
2D-Rotational Motion (in progress)
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Particle on a ring: Schrodinger Equation
  2 d 2 ( )
 E ( ) …………….. Second order differential equation
2I d 2

Solve the Schrodinger equation and apply the boundary conditions

 m ( )  Ae im (derivation not in syllabus)

• Wavefunction should be a periodically varying function

Cyclic Boundary conditions: (ϕ) = (2π + ϕ)
im im (  2 )
Ae  Ae
e im  e im e im 2
1  e im 2
1  cos 2m  i sin 2m
2m = 0,  2   4   6 ….
m = 0,   ….
The wavelength  should fit to the circumference 2r of
the circle. m = 2r
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Particle on a ring: Wavefunction

Wavefunction for particle on a ring:  m ( )  Ae im

(derivation not in syllabus)

Normalization
2


im im
A( e ) * A( e ) d  1
 m ( ) m ( ) 2 0
2


im im
A( e ) A( e ) d  1
0
Normalized Wavefunction: 2

 d  1
2
A
eim
 m ( )  0

2 1/ 2
A
1
2
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Particle on a ring: Energy

  2  2 ( )   2  2  e im 
Schrödinger equation   
2I  2
2 I  2  2 1/ 2 
m 2 2
  ( )
2I
L2z m 2  2
Energy of particle on a ring: E   Energy levels
2I 2I (Quantized)
m = 0,   ….

• Degeneracy: All levels with ml ≠0 are doubly degenerate i.e., there

are two states of the same energy. The two states differ in the sense of
rotation.
• No zero point energy. with ml = 0 ; Ground state nondegenerate.
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Particle on a ring: Wavefunctions

e 2i
  2 ( ) 
2  1/ 2

e 1i
 1 ( ) 
2 1/ 2

1
 0 ( ) 
2 1/ 2
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 2D-Rigid Rotor
Wavefunction & Probability Density

 m ( )  m ( ) 2

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Particle on a ring: Momentum Lz

Lz ml      m      1 eim

i    i    2 1/ 2

 1 im
 im e  m m
i 2 1/ 2

Quantized values of
Angular momentum:  m angular momentum

 The solutions of the Schrödinger equation,

eigenfunctions of the Hamiltonian operator, are
also eigenfunctions of the angular momentum
operator Lz

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Example 6: Application of Quantum Mechanics
to particle on a Sphere (3-D Rigid Rotor)
Rotation in three dimensions
• A particle could be considered as if moving on the surface of a sphere.

• Rotational motion in three dimensions could be a mimic of

electrons around nuclei in atoms. (except that particle here is at fixed
distance r )
V=0
• Two angles (particle confined to a spherical space)
 - the azimuthal angle
z
 - the colatitude
 x, y, z    ,  
• Motion of a particle over sphere is like r y
motion of particle over a stack of rings, with
additional freedom to migrate between rings.
  ,        x

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Hamiltonian operator in polar coordinates

ˆ  2
H   2  Vˆ
2m
  2
 2
 2

   2 
2
 2  …….. Cartesian coordinates
x y z 
2

  2
2  1  1 2 1     
 
2    2  2   sin  
r    
r r r  sin    sin    
2 2

(Don’t memorize)
Since r is fixed

1  1 2 1     
  2
2
 2   sin   ……..
r    
polar coordinates
 sin    sin    
2

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Particle on a sphere rigid rotor:
Boundary Conditions
  ,       
• Two variables involved: Polar angle  & Azimuthal angle ϕ
• Imposing first boundary condition: The acceptable wavefunction
must be described as the particle travel round the equator
(similar to particle in a ring)
Such that ϕ = 0 to 2π and the acceptable solution should introduce a
quantum number, ml
• Imposing second boundary condition: The acceptable
wavefunction must be described as the particle travel across the
poles.
Such that ( = 0 to π); This constraints introduces a second quantum
number l, called orbital momentum quantum number.

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Particle on a sphere rigid rotor:
Acceptable solution of wavefunction
• The acceptable solution of wavefunction:
 l ,m  ,   = Yl,m ( , ϕ) = Θl,ml( )Φml(ϕ)
l l

Spherical harmonics iml

e
Yl,ml( , ϕ)  Polynomial l ,ml ( ).
such that
2  1/ 2

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.
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Particle on a sphere rigid rotor:
Acceptable solution of wavefunction
•Yl,ml could be imagined as wave like distortions on a
spherical shell.
l ml Yl,ml( , ϕ)
0 0
1 0
±1
2 0
±1
±2
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