1

Angular Momentum
Classical Angular Momentum
v v v
v v
Recall the classical definition for angular momentum. L r p mr v

r
L

Quantum mechanically, angular momentum operator can be expressed as similarly in terms

of the position and velocity operators.
L r p
For a particle constrained to the x-y plane
L rp
2

p 2 L
1
L2

2m r
2m 2mr 2
Recall the definition for the moment of inertia: I mr 2
TE

Therefore, the energy of particle rotating in a plane can be written as E

L2
2I

Quantization of Angular Momentum

Recall the deBroglie relationship p

rh

Thus, as the particle is moving on the ring it travels as a wave.

A particle rotating in a plane has a wavelength. L r p

- unless momentum has correct value, the wave will destructively interfere with itself
- constructive interference occurs only at discrete values of
- circumference of ring is 2r.

2r
m

where m is an integer.

Rearrangement yields
r

m
2

Substitute into the deBroglie relationship.

r h h m
L

mh
2
**Thus, we realize that a particle with angular momentum and wave-like properties must
have its angular momentum quantized.**

Particle-on-a-Ring

Note that for this model, the particle has a single degree of freedom which is the angle, .
Schrdinger Equation
The potential energy function for a particle-on-a-ring is
V r {0 ififr0RrR, r R

Note: V 0

Therefore the Schrdinger equation is

h2 1 2
h2 2
2 2IE
E
E 0
2 0
2m r 2 2
2I 2
2
h
2IE
2
Let 2 m
h
2
2
2IE

2 0
m 2 0 D 2 m 2 0
2

h
2

m 2 0 im

Particle-on-a-Ring Wavefunction
The normalized solution for a particle-on-a-ring is
1 im
2IE
m
e
where m
2
h2
Particle-on-a-Ring Energies

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m 2 h2 L2
The energy level for a particle-on-a-ring can be written as. E

2I
2I
- Note again that L mh
Quantization of a Particle-on-a-Ring
To make the wavefunction physically meaningful, we can apply a boundary condition to the
solution, that is m 2 m .
1 im 2
1 im
1 im im2
1 im
e

e
e e

eim2 1
2
2
2
2
The above boundary condition can only be satisfied when m 0, 1, 2, 3,...
Thus, quantization is imposed by requiring the requirements of the wavefunction.
*Therefore, two simple arguments can be found for the quantization of angular momentum.*

Particle-on-a-sphere (Rigid Rotor)

z
(R , , )

R
R s in

Now the particle has two degrees of freedom, , .

Schrdinger Equation
The potential energy function for a particle-on-a-sphere is
V r {0 ififr0RrR, r R

Note: V , 0

Therefore the Schrdinger equation is

h2 1 2
1

sin
2
2
2I sin
sin

E 0

To begin to solve the equation, we will employ the separation of variables technique.
First we will assume a solution of the form ,
h2
2I

2

1
1

sin

2
2

sin

sin

Allow the differential operators to operate.

2

h2
1
1

sin

2I
sin 2 2
sin

E 0

E 0

h2
2I
sin 2
2

1 sin
2IE 2

sin
2 sin 0
2



h

Now divide each side of the equation by

Separate terms with from terms with .

2

sin
2IE 2
1
sin
2 sin


h
2
Let each side of the equation be equal to a constant.
2

sin
2IE 2
1
sin

sin

m2

h2
2
Note: It will be convenient to make the perspicacious choice -m2 as a constant rather than
m to find the solution to the differential equation.
Now the two-variable differential equation above can be split into two separate singlevariable differential equations.

sin
2IE 2
2
sin
2 sin m 0


h
2
1
m2 0
2

The equation can be rewritten as

2
m2 0
2

The solutions are the same particle-on-a-ring solutions with the same restrictions on the m
quantum number.

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m

1 im
e
2

We make another perspicacious choice for a constant: Let

2IE
l l 1
h2

By dividing by sin2, and multiply by (), the equation can be rewritten as

1
m2
sin
l l 1 2 0
sin

sin

Finally, allow the

operator to operate

2 cos
m2

l
l

0
2
sin
sin 2

Associated Legendre Equation

In the late 18th century, French mathematician Adrien-Marie Legendre found the solution the
for the below equation.

1 x
2

d2P x
dP x
m2

2x

l
l

P x 0
dx 2
dx
1 x 2

The solutions, P(x), are finite only if P(x) remains between 1 and 1 and the values of l = 0,
1, 2, 3, and m = 0, 1, 2, , l.
Given the above condition, one can make the substitution for x, x = cos and manipulate the
associated Legendre equation and make it identical to the equation being discussed above.
In other words, the equation is the associated Legendre equation.

The solutions to the associated Legendre equation are the associated Legendre polynomials,
Plm x .
l

Plm x

0
1
1

0
0
1

1
x

1
cos
sin

1
3x 2 1

3x

15 1 x 2

1
35x 4 30x 2 3
8
5
7x 3 3x 1 x 2

2
15
7x 2 1 1 x 2

1 x
2

1
3cos 2 1

2
3cos sin

1 x
3 1 x
1
5x 3x
2
2

3sin 2

3
5x 2 1 1 x 2

2
15x 1 x 2

15sin 3

1 x
105 1 x

2 3

105x

2 2

1
5cos3 3cos

2
3
5cos 2 1 sin

2
15cos sin 2

1
35cos4 30 cos2 3
8
5
7 cos3 3cos sin

2
15
7 cos 2 1 sin 2

2
105cos sin 3
105sin 4

m
Emphasis should be made that the l functions depend on l and m which are numbers
that can only be discrete values. Thus the angular momentum for a particle-on-a-sphere
remains quantized.

Particle-on-a-Sphere Wavefunction
The normalized solution for a particle-on-a-sphere are called the spherical harmonics.
The spherical harmonics are simply the normalized product of the functions and the
functions.

, Ylm , N lm lm m where N lm is a normalization constant

One can think of the spherical harmonics as the set of possible standing waves on a sphere.
Y00 ,

1
4

Y10 ,

1
2

1
2

5
Y20 ,

16
15
Y21 ,
8

1
2

15
Y ,

32
2
2

Y11 ,

cos

3cos

sin e
2

1
2

Y11 ,

sin ei

1
2

sin e i

sin cos ei
1
2

2i

15
Y21 ,
8
15
Y ,

32
2
2

1
2

sin cos e i
1
2

sin 2 e 2i

- We shall soon see that the spherical harmonics dictate the shape of orbitals in a
hydrogen atom.
Particle-on-a-Sphere Energies
The energy level for a particle-on-a-sphere can be written as. E
2
2
- Note that L l l 1 h

l l 1 h2 L2

2I
2I

Eigenvalues of Angular Momentum Operators

L 2
T
2I

Since spherical harmonics are eigenfunctions of T , they are eigenfunctions of L 2 .

m
- Note Yl , are not eigenfunctions of L .
2
L 2 is proportional to p which to proportional to T .

L 2 h2

1 2
1

2 2 2

sin h r
2
2

sin sin
L 2 Ylm , h2 l l 1 Ylm ,

Spherical harmonics are also eigenfunctions of L z

L z ih x y ih
x

y
L z Ylm , mhYlm ,
2
It can be shown that L , L z 0 , L2 and Lz can be known at the same time.
However, L x , L y ihL z 0 . Also L y , L z ihL x 0 and L z , L x ihL y 0
Thus only one component of the angular momentum can be known as a time.
- If Lz is known, then Lx and Ly are completely undetermined.

Vector Model of Angular Momentum

z
L

v
L L2 h l l 1
v
L z mh

L
y

Since Lx and Ly are completely unknown, we can think of the

angular momentum vector as precessing about the z-axis.
- Caution! One should not take the precession too literally.
v
The angular momentum vector, L , sweeps out a cone in space
v
with the axis of the cone being the L z vector.
Later, we will consider how angular momenta add together and
vector model will be very helpful.

Spin
Many particles (including e-) have intrinsic angular momentum.
For lack of better word, we call it spin angular momentum.
The eigenvalues of spin are similar to orbital angular momentum.
However, the wavefunctions and the operators that describe spin are much different.
The wavefunctions that describe spin are called spin functions or spinors.
- More about spinors when we discuss the hydrogen atom.
Electron Spin
Electron spin has one l value that is relabeled as s. s

1
2

Electron spin has two m values that are relabeled as ms. ms

1
2

1 1
3
S 2 h2 s s 1 h2 1 h2
2 2
4
1
S z ms h h
2
Nuclear Spin
1
2
Because nucleus is composite particle(made of quarks and gluons), predicting spin is very
difficult (impossible).
Both proton and neutron have s

Experimentally measured spins found for naturally occurring nuclei.

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1 3 5 7 9
s 0, ,1, , ,3, , 4, ,5, 6, 7
2 2 2 2 2
Possible values for ms.
ms s,s 1,s 2,..., s 1 , s
Eigenvalues of nuclear spin same as electron spin!!
S 2 h2 s s 1
S z ms h
We will come back to nuclear spins during discussion of nuclear magnetic spectroscopy.