Lecture 6: CHM112M/CHM102A

Mainak Sadhukhan

1
 This note is NOT an alternative to the lectures. This note will help you to recollect
the main points taught in the lectures and also sometimes to expand your horizon. This
note alone will not be helpful to you unless you attend the lectures and tutorials. Also
please feel free to talk to tutors and instructors for any trouble whatsoever regarding
the course. We will definitely help you!

2
1 Rotational motion of a molecule
In last class we started discussing the quantum mechanics of rigid rotor.

Figure 1: Schematic diagram of a rigid rotor.

For this system, the moment of inertia I = µr2 . For the quantum rigid rotor, first
we need to construct a angular momentum operator since, the Hamiltonian for the rigid
rotor is
Lˆ2
HRR = + V̂ (1)
2I |{z}
0

From classical mechanics we know,

êx êy êz

L = r × p = (x̂, ŷ, ẑ) × ( p̂x , p̂y , p̂z ) = x y z . (2)
p̂x p̂y p̂z

where (êx , êy , êz ) represent the unit vectors along x, y and z-directions, respectively.
Consequently,
Lˆ2 = Lˆx2 + Lˆy2 + Lˆz2 (3)
where

L̂x = (ŷ p̂z − ẑ p̂y ) (4a)

L̂y = (ẑ p̂x − x̂ p̂z ) (4b)
L̂z = (x̂ p̂y − ŷ p̂x ). (4c)

Since we are dealing with spherically symmetric motion (all three spatial Cartesian
coordinates are equivalent), we will now use spherical polar coordinate system (see
Fig. 2).

3
Figure 2: Connection between Cartesian (x, y, z) and spherical polar coordinates
(r, θ , φ ). Note that the angles θ and φ are measured in relations to Cartesian coor-
dinates z and x, respectively. Also θ ∈ [0, π] and φ ∈ [0, 2π] spans whole surface of a
sphere of radius r.

The conversion between Cartesian and spherical coordinates are straightforward :

x = r sin(θ ) cos(φ ), (5a)

y = r sin(θ ) sin(φ ), (5b)
z = r cos(θ ). (5c)

Using Eqs. (5) and Eqs. (4), we obtain the polar forms of angular momentum operators:

 
∂ ∂
L̂x = −i} − sin(φ ) − cot(θ ) cos(φ ) (6a)
∂θ ∂φ
 
∂ ∂
L̂y = −i} cos(φ ) − cot(θ ) sin(φ ) (6b)
∂θ ∂φ
∂
L̂z = −i} . (6c)
∂φ
Combining Eqs. (6) and Eq. (1) we obtain the TISE for rigid rotor as

−}2 ∂2
   
1 ∂ ∂ 1
sin(θ ) + 2 ψ(θ , φ ) = Eψ(θ , φ ) (7)
2I sin(θ ) ∂ θ ∂θ sin (θ ) ∂ φ 2
Since the rotor is “rigid” meaning the radial distance r between the reduced mass µ and
the centre-of-mass does not change, angular variable θ and φ are the only variables of
motion. Consequently, this equation describes the motion of a particle moving freely
on the surface of a sphere of radius r 1 .
1 How many quantum numbers do you expect to define the system’s motion completely?

4
 Just like the harmonic oscillators, we will skip the mathematical derivation of the
solution of Eq. (16) and only analyze the solutions. Solution of Eq. (16) provides
eigenfunction
ψ(θ , φ ) = Yl,ml (θ , φ ) = Pl,ml (θ )eiml φ (8)
where, Pl,ml (θ ) are polynomials called associated Legendre polynomials and Yl,ml (θ , φ )
are called the spherical harmonics2 Possible values of l and ml are

l = 0, 1, 2, . . . (9)
ml = 0, ±1, ±2, . . . ± l (10)

A few first spherical harmonics are shown below:

l ml Yl,ml

0 0 √1
4π
1 -1 − √38π sin(θ )e−iφ
1 1 √3 sin(θ )eiφ
8π
1 0 √3 cos(θ )
8π

Table 1: Table of first few spherical harmonics.

As we shall soon see that these spherical harmonics are quintessential to under-
stand Hydrogenic orbitals.
The energy of a quantum mechanical rigid rotor is given by

}2
El = l(l + 1) (11)
2I
Surprisingly, the energy does not depend on ml . Therefore, for any given l, all corre-
sponding states with different ml values will have same energy! The rigid rotor energy
levels are therefore (2l + 1)-fold degenerate.
The difference between consecutive energy levels is therefore

}2
∆El = El+1 − El = (l + 1) (12)
I
Clearly, the spacing increases with quantum number l.
Also note that, the “classical magnitude” of angular momentum of a certain state
l2 2
can be calculkated by equating classical ( 2I ) and quantum energy (l(l + 1) }2I )as
p
L |l| = l(l + 1)}. (13)
2 The solutions of Laplace’s equation are generally called harmonic functions as they can be expressed

by sine and cosine functions which describe a harmonic motion. The term spherical refer to the fact that,
for a given l, these functions provide a complete basis for motion in the surface of a sphere(vide spherical
harmonics addition theorem).

5
 It is also interesting to note that Yl,ml are not only eigenvectors for Lˆ2 operator, but
also are eigenvectors for L̂z operator:

L̂zYl,ml (θ , φ ) = ml }Yl,ml (θ , φ ) (14)

Clearly, this indicates that the energy and z−directional angular momentum can be
measured simultaneously. However, given a certain eigenvalue for Lˆz , one cannot
determine the rotor’s angular momentum along x or, y-directions. Here one should
remember that the z-direction is not special. It is just one of the three orthogonal direc-
tions. Intuitively, that means that two orthogonal components of angular momentum
may not be measured simultaneously. Indeed,
h i h i h i
Lˆ2 , L̂x = Lˆ2 , L̂y = Lˆ2 , L̂z = 0 (15a)
 
L̂x , L̂y = i}L̂z (15b)
 
L̂y , L̂z = i}L̂x (15c)
 
L̂z , L̂x = i}L̂y (15d)

Due to this reason, the angular momentum vector is normally shown as a cone along
z-axis, its tip moving in a circular ring (see Fig. 3).

Figure 3: The visualization of angular momentum and its z-component.

2 Polar plots
In last class we obtained the TISE for rigid rotor as

−h̄2 ∂2
   
1 ∂ ∂ 1
sin(θ ) + 2 ψ(θ , φ ) = Eψ(θ , φ ) (16)
2I sin(θ ) ∂ θ ∂θ sin (θ ) ∂ φ 2

Solution of Eq. (16) provides eigenfunction

ψ(θ , φ ) = Yl,ml (θ , φ ) = Pl,ml (θ , φ )eiml φ (17)

6
where, Pl,ml (θ , φ ) are polynomials called associated Legendre polynomials. Possible
values of l and ml are
l = 0, 1, 2, . . . (18)
ml = 0, ±1, ±2, . . . ± l (19)
As one can see that the wave function is expressed in terms of the angles θ and
φ . Therefore to visualize the wave function, we need to employ so-called “polar plot”.
For simplicity we will see an example for Y1,0 (θ , φ ) ∝ cos(θ ). In polar plots, the
coordinates are plotted in the angular grid as shown in Fig. 4. The distance between
the origin and a point in the curve represent the value of the function at that θ . The
parity (positive and negative) of the function is represented by different colors.
π
π 7π 5π
7π 5π 2
2π 12 12 π
2
2π 12 12 π
3 3
3 3 3π π
3π π
4

| Ψ(θ, ϕ) |
4
4 4
5π π
5π π

θ
6 6

+ +
6 6

− +
11 π π
11 π π 12 12
12 12

π 0
π 0

13 π 23 π
13 π 23 π 12 12
12 12
7π 11 π
7π 11 π 6 6
6 6 5π 7π

5π 7π 4 4
4π 5π
4 4
4π 5π 3 17 π 19 π 3
3π
3 17 π 19 π 3 12 12
3π 2

| Ψ(θ, ϕ) | = | Yl=1,m=0(θ, ϕ = 0) |
12 12

P(θ, ϕ) = | Ψ(θ, ϕ) |2 = | Yl=1,m=0(θ, ϕ = 0) |2

2

ϕ ϕ

Figure 4: Polar plot along a cross section of φ (above) and complete angular depen-
dence of rigid rotor wave function Y1,0 . Red and blue colors represent the positive and
negative signs of the function. For probability density both “lobes” are positive and
colored green.

The energy of a quantum mechanical rigid rotor is given by

h̄2
El = l(l + 1) (20)
2I

3 H-like atoms
Having discussed quantum mechanics of a few mechanical systems, we will now dis-
cuss the quantum mechanical treatment of so-called “Hydrogenic atoms” viz. an elec-
tron (charge = e and mass = me ) interacting with a positive nucleus of charge Ze and

7
mass M via Coulomb interaction. Henceforth, we will use R and r to denote position
vectors of nucleus and electron, unless mentioned otherwise. See Fig. 5 for under-
standing the reference frame.

Figure 5: An electron with charge e around a nucleus with charge Ze.

The Hamiltonian of such a system is

h̄2 2 h̄2 2 Ze2

HH = − ∇R − ∇ − (21)
| 2M
{z } 2me r 4πε0 |R − r|
| {z } | {z }
nuclear kinetic energy electronic kinetic energy electron-nucleus attraction

where ε0 is vacuum permittivity. Just like SHO, we can decouple the motions for this
two-body system in two independent coordinates: center of mass and relative coordi-
nates. Consequently, we can write the Hamiltonian in polar coordinate system as

h̄2 ∂ 2 1 ∂2 1 e2
  
2 ∂ 1 1 ∂ ∂
H (r, θ , φ ) = − 2
+ + 2 2 2
+ sin θ −
2µ ∂ r r ∂r r sin θ ∂ φ sin θ ∂ θ ∂θ 4πε r
(22)
and the TISE can be solved by separation of variables

ψ(r, θ , φ ) = R(r)Y (θ , φ ) (23)

. The angular part is identical to spherical harmonics discussed in the rigid rotor prob-
lem. The radial part R(r) is dependent on two quantum numbers, the principal quantum
number n and the azimuthal quantum number l, which also appears in the angular part.
Thus we have
ψn,l,ml (r, θ , φ ) = Rn,l (r)Yl,ml (θ , φ )
Let us see how Rn,l (r) looks like. For convenience we define ρ = 2r/na0 where

h2 ε0
a0 =
πme e2
is referred to as the Bohr radius and is equal to 0.529 . The radial part of the wavefunc-
tion can now be written as

Rn,l (r) = Nn,l ρ l Ln,l (ρ)e−ρ/2 (24)

8
where Ln,l (ρ) is the associated Laguerre polynomial with degree n − 1 and Nn,l is the
normalization constant. The first few wavefunctions are given below:

n = 1, l = 0, 1s orbital ψ1,0,0 = R1,0 (r)Y0,0 (θ , φ )

 3/2  1/2
1 −r/a0 1
= 2 e
a0 4π

n = 2, l = 0, 2s orbital ψ2,0,0 = R2,0 (r)Y0,0 (θ , φ )

 3/2    1/2
1 1 r −r/2a0 1
= 1/2
2 − e
8 a0 a0 4π

n = 2, l = 1, ml = 0, 2pz orbital ψ2,1,0 = R2,1 (r)Y1,0 (θ , φ )

 3/2
r −r/2a0 3 1/2
 
1 1
= e cos θ
241/2 a0 a0 4π

n = 2, l = 1, ml = 1, 2p1 orbital ψ2,1,0 = R2,1 (r)Y1,0 (θ , φ )

 3/2
r −r/2a0 3 1/2
 
1 1
= e sin θ eiφ
241/2 a0 a0 4π

n = 2, l = 1, ml = −1, 2p−1 orbital ψ2,1,0 = R2,1 (r)Y1,0 (θ , φ )

 3/2
r −r/2a0 3 1/2
 
1 1
= e sin θ e−iφ
241/2 a0 a0 4π

The last two are combined to give the real 2px and 2py orbitals.
The energy of a state, however, depends only on the principal quantum number n
and is given by
me e4
En = − 2 2 2 (25)
8h ε0 n
The restrictions on the quantum numbers are as follows:

n = 1, 2, 3, ... l = 0, 1, 2...n − 1 ml = 0, ±1... ± l

and they are referred to as principal, azimuthal and magnetic quantum numbers. The
wavefunction ψn,l,m is the wavefunction of a single electron and is referred to as an
orbital or a spatial orbital.
For each n we have n number of l -degeneracy and for each l we have 2l +1 number
of ml values. The degree of degeneracy for an energy level can therefore be computed
as
n−1
gn = ∑ 2l + 1 = n2 (26)
n=0