General Chemistry (CHEM

F111)

Lecture-7
30/01/2024
Recap

1. Solutions to Schrodinger equations for

a particle in 2D sqaure box

2. Tunneling effect
Scanning Tunneling Microscopy (STM)

3. Vibration-Harmonic Oscillator
Today’s topic
-Particle on the sphere: rigid rotor
Quantization of orbital angular momentum
Space quantization

-Hydrogenic atom
Rotation on a sphere–rigid rotor
Particle constrained to rotate on a surface of sphere
of radius r (fixed).
Hamiltonian for motion in three dimensions:

Ĥ = - (ħ2/2m)2 + V

2 is called laplacian.

2 = 2/x2 + 2/y2 + 2/z2

Ĥ = E
- (ħ2/2m)2 = E
V = 0 (particle confined to a spherical space).
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 Rotation on a sphere–rigid rotor
It is convenient to describe the solutions to the
Schrodinger equation in spherical polar
coordinates (r, ,) rather than cartesian (x,y,z)
Spherical polar coordinates
Rotation on a sphere–rigid rotor

Laplacian in spherical polar coordinate:

2 = 2/r2 + (1/r)(/r) + (1/r2)(2)

2 is called legendrian.

2 = (1/Sin2)(2/2) + (1/Sin)(/)Sin(/)
We have, - (ħ2/2m)2(,) = E(,)
Note:  is a function of  and , not r (as r is constant).
Since r is constant, - (ħ2/2m)(1/r2)[2(,)] = E(,)

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Rotation on a sphere–rigid rotor

- (ħ2/2m)(1/r2)[2(,)] = E(,)

Or, 2 (,) = - (2mr2E/ħ2)(,) = - (2IE/ħ2)(,)

Or, 2(,) = - (,)
where  = 2IE/ħ2
(,) is separated into  part and  part, i.e.
(,) = ()()
Therefore,
(1/Sin2)[2()/2] + (1/Sin)(/)Sin[()/]
= - 

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Rotation on a sphere–rigid rotor

(1/Sin2)[2()/2] + (1/Sin)(/)Sin[()/]
= - 
Or, (/Sin2)[d2/d2] + (/Sin)(d/d)Sin[d/d]
= - 
Multiplication of both sides by Sin2/, and
rearrangement gives,

(1/)[d2/d2] + (Sin/)(d/d)Sin[d/d] + Sin2 = 0

Depends only on  Depends only on 

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Rotation on a sphere–rigid rotor
Say  dependent part, (1/)[d2/d2] = - ml2 ………. (1)

And  dependent part, Sin/)(d/d)Sin[d/d] + Sin2

= + ml2 ……… (2)

The first equation involves azimuthal angle  as variable.

The solution of the Eq.1, (1/)[d2/d2] = - ml2 with the

application of cyclic boundary condition is known to us.
Wavefunction is specified by the quantum number, ml
with ml = 0,   ….

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Rotation on a sphere–rigid rotor
•The solution to the second equation (Eq. 2)
(involves the polar angle θ) is much more
complicated.
• The cyclic boundary conditions on θ results in
the introduction of a second quantum number, l
which gives acceptable solutions.
• The presence of ml in the Eq.2 implies that the
range of acceptable values of ml is restricted by
the value of l.
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Rotation on a sphere–rigid rotor
• The solution of Schrodinger eq. shows that the
acceptable wavefunctions are specified by two
quantum numbers l and ml which are restricted
to the values
l (orbital angular momentum quantum no.) =
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
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Rotation on a sphere–rigid rotor

On solving, and imposing the appropriate

boundary conditions, obtain the normalized
wavefunctions, Yl,ml(,), characterized by two
quantum numbers l and ml and are called
‘spherical harmonics’.
•The spherical harmonics are a product of two
functions, Yl,ml(,) = Θlml(θ)Φml(φ)

•The functions Φml(φ) contain ml = 0, ±1, ±2,…

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Rotation on a sphere–rigid rotor
Spherical harmonics, Yl,ml(,).
l ml Yl , ml
1/2
 1 
0 0  4 
 
1/2
 3 
1 0  4  cos 
 
1/ 2
 3 
1   sin  e  i
 8 

1/ 2
 5 
(3cos 2   1)
2 0  16 
 
1/ 2
 15 
 cos  sin  e  i
1 
 8 
1/2
 15 
sin 2  e 2i
2  32 
 

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Rotation on a sphere–rigid rotor

The solution of Schrodinger eq. also gives the

energy, E of the particle restricted to the values:
E = l(l+1)(ħ2/2I) l = 0,1,2,3……….
Energy is quantized and is independent of ml.

A level with quantum no. l is (2l+1) fold

degenerate.
Degeneracy = (2l+1)

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Rotation on a sphere–rigid rotor
Classically, Energy, E = J2/2mr2 = J2/2I
Energy, El = l(l + 1)ħ2/2I
Comparing we get
J2 = [l(l + 1)]ħ2
Therefore, J = [l(l + 1)]1/2ħ l = 0,1,2,3…..
Magnitude of angular momentum = [l(l + 1)]1/2ħ

with l = 0,1,2,3..
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Rotation on a sphere–rigid rotor
The angular momentum about the z-axis is also
quantized
Z-component of angular momentum = mlħ
ml = l, l-1,……,-l
The component of angular momentum about the z-axis
takes only 2l+1 values.

Two aspects of the quantization of angular momentum

vector, the magnitude and its orientation.
The orientation of a rotating body is quantized. Space
quantization. BITSPilani, Pilani
Rotation on a sphere–rigid rotor
Case l = 1, ml = 1, 0, -1

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Rotation on a sphere–rigid rotor

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

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Rotation on a sphere–rigid rotor

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

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Rotation on a sphere–rigid rotor
Case l = 3, ml = 3, 2, 1, 0, -1,
-2, -3

(a) The angular momentum of a particle with l = 3. (b) The seven orientations
of the angular momentum vector. (c) The cones representing possible but
unspecified orientations around the z-axis.

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Hydrogenic atom
Atom with a nucleus of charge Ze and mass mN, and a single
electron of charge – e and mass me. The two interact according to
the Coulomb potential
V(r) = – Ze2/r
where r is the distance of electron from nucleus, and  is the
vacuum permittivity.
Since mN >> me, the nucleus may be taken to be at rest, and the
electron moving about it.
Note that the potential is spherically symmetric, ie., it depends
only on the distance r
Other example: He+ (Z=+2 and one electron), Li2+ , Be3+ , C5+ etc.
Exact Solution of Schrodinger equation is possible ! BITSPilani, Pilani Campu
Hydrogenic atoms
The Hamiltonian for internal motion of the electron
relative to the nucleus is
Ĥ = - (ħ2/2)2 + V

= reduced mass = me×mN/(me+mN)

V = - (Ze2/4or)

2 = 2/x2 + 2/y2 + 2/z2

2 is called laplacian.

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 Spherical Polar Coordinates
Given the spherical symmetry of the potential V, the Schrodinger
equation is most conveniently treated in spherical polar
coordinates by the separation of variables method.

 2 2 Ze 2 
     ( x, y, z )  E ( x, y, z )
 2m 4 0 r 

Particle in a sphere