Advanced Quantum Mechanics, Notes based

on online course given by Leonard Susskind

- Lecture 3

Atomic Orbits and Harmonic Oscillators

Review Plus

What is angular momentum about?

Classically could be a particle moving in a central force field

3D postion defined by r and 2 angles

Quantum Mechanically particle described by a wave function.

Angular momentum has to do with the angular dependence of the wave function

In general wave function in situation like above is ψ(r,θ,ϕ)

In 2D angular momentum is just the generator of rotation about the perpendicular axis
∂
L=-i
∂θ
and tells you how the wave function changes with angle

∂ψ(r ,θ)
ψ eigenvectors satisfy -i = l ψ(r,θ)
∂θ

r is ‘spectator’
ilθ
Solution is ψ=e r l is and integer as ψ(0)=ψ(θ)
Doesn’t matter what the r dependence is, it will be an angular momentum eigenstate.
Radial dependence relevant to energy but not to angular momentum

Similary in 3D - angular momentum has to do with the angular dependence of the wave function

ψ(r,θ,ϕ) = X(r) Y(θ,ϕ)

content from lecture by Leonard Susskind

2 | AQMLecture3.nb

Y determines the angular momentum eigenstates

Awkward to think of θ and ϕ so we’ll use some tricks

Recall: Lz, Lx , Ly commutation relations [Lx ,Ly ]=iLz etc

Pick one and work with it as a basis, we pick Lz

Lz|m>=m|m>

Define L+ =Lx + iLy L- =Lx - iLy and use them to generate other eigenstates
L+ |m>= m + 1 |m+1> (sometimes just writes this as L+ |m>=|m+1> )

Might come to an end eg L+ |m>=0 L- |m>=0

If rotationally invariant then any termination must be the same amount above and below origin
2 ways to satisfy this:
1. Integer spacing going up and down from 0
1 1
2. Integer spacing going up and down from and -
2 2

For integer case: max value of m is called l and the minimum -l

Number of states is 2l+1, called a multiplet of states

Multiplets

All states of a multiplet have the same energy

Magnitude of angular momentum is from L2 = L2x + Ly2 + Lz2 as in Classical Mechanics but these are
no longer numbers, they are operators

Classically: L2 = Lz2 + (Lx - iLy ) (Lx + iLy )

but in QM Lx and Ly dont commute ie [Lx ,Ly ]=iLz so
L2 = Lz2 + (Lx - iLy ) (Lx + iLy ) - i [Lx ,Ly ]
= Lz2 + (Lx - iLy ) (Lx + iLy ) - i iLz
= Lz2 + L- L+ + Lz

If we apply this to the maximum state l remembering Lz|l>=l|l> and L+ |l>=0

L2 |l> = Lz2 |l> + Lz|l> + L- L+ |l>

= l 2 |l> + l|l> + L- 0
= l (l + 1) |l>

All states in multiplet have same L2 but have different projections onto the z axis and in QM these
are quantised.

content from lecture by Leonard Susskind

 AQMLecture3.nb | 3

Exercise to show all states in multiplet have same L2

L2 |l> = = l (l + 1) |l>
so want to show that other states in the multiplet have the same eigenvalue eg
L2 |l - 1> = = l (l + 1) |l -1>

First find commutation relations for L2 remembering

[Lx ,Ly ]=iLz and [Ly ,Lz]=iLx and [Lz,Lx ]=iLy

[L2 ,Lx ]= [Lx Lx ,Lx ] + [Ly Ly ,Lx ] + [LzLz,Lx ]

= [Ly Ly ,Lx ] + [LzLz,Lx ]
= Ly [Ly ,Lx ] + [Ly ,Lx ]Ly + Lz [Lz,Lx ] + [Lz,Lx ]Lz
= Ly (-iLz) +( -iLz)Ly + Lz iLy +iLy Lz
=0

And simlarly for [L2 ,Ly  and [L2 ,Lz]. Since L2 commutes with Lx Ly and Lz so must also commute
with L+ L-

Back to:
L2 |l> = l (l + 1) |l>
L- L2 |l> = l (l + 1)L- |l>
L2 L- |l> = l (l + 1)L- |l> as L2 commutes with L-
L2 L- |l> = = l (l + 1)L- |l>
L2 |l-1> = = l (l + 1) |l-1>
So state |l-1> has the same eigenvalue as |l>

We can continue up and down the multiplet to show it is true for whole multiplet.

We now have eigenvectors for L2 and for Lz

And functions of the angles with eigenvectors characterised by m and l

These functions are Yl m(θ,ϕ), called spherical harmonics

Are the analogs on a sphere to e±il θ

on a circle

Dont need to work out the detailed functions to progress, just need to know:
1. There are 2l + 1 of these Yl m(θ,ϕ) for each value of l
2. In these m ranges from l to -l and L2 = l ( l + 1)

In atomic physics all states with the same angular momentum have the same energy since L2
commutes with H at least for central force problem

content from lecture by Leonard Susskind

4 | AQMLecture3.nb

0:36:08 Central Force Problem

We’ll use classical physics to make guesses to help solve this for quantum situation

 2
p
Want to solve Schrodinger equation for H = + V(r)
2m

p stands for the 3 components of momentum
V(r) is a central force depending on r only

Classically: angular momentum conserved where ever you have rotational invariance (similar to
having momentum conservation when you have translational invariance, Noether’s theorem)

  
L = r x p magnitude and direction conserved

Plane of orbit also conserved, once we know this and rotational invariance then we might as well
put our orbit in the x y plane to make things simpler

Orbit (r) doesn’t have to be a circle or closed; momentum may or may not be perpendicular to r

p pθ
pr
r

Momentum has 2 components; one along r (pr ) and one along θ (pθ )

p2 = pr2 + pθ2

pr2 +p2θ
H= + V(r) (1)
2m

Magnitude of angular momentum

L2
|L| = |pθ | |r| or L2 = pθ2 r 2 pθ2 = (2)
r2

Using (1) and (2)

pr2 L2
H= + + V(r)
2m 2 mr2

content from lecture by Leonard Susskind

 AQMLecture3.nb | 5

0:46:03
1
Forces push you to smaller energy; is centrifugal force pushing you away from the origin
r2

If something comes in with a certain angular momentum it can’t get too close to the origin due to the
1
r2

1
If L=0 then there is no element and course is backwards and forwards through the origin
r2

-1
V(r) is proportional to eg attraction between an electron and a proton
r

1 1
Plot of how and parts combine
r2 r

0.2

1
-
r
2 4
Oscillate between max
6 8 10 12 r 14
1

and min r - an ellipse r2

1 1
-0.2 - +
r r2

-0.4 for simplest orbit r doesn't change

- circle

0:50:38 Now look at the Quantum Mechanics point of view

Instead of a particle we have wave funtion ψ(r,θ,ϕ)

if we know the angular momentum we know we have a spherical harmonic Yl m(θ,ϕ)

pr2 +p2θ ∂
Hψ(r) = Eψ(r) and earlier equation H = + V(r) and pr = i ℏ
2m ∂r

Lead us to:
ℏ2 ∂2 ℏ2 l (l + 1
(- + + V(r)) ψ(r) = E Ψ(r)
2 m ∂r 2 2 mr2
eg m might be mass of electron

Solutions are eigenvectors of energy with given angular momentum and the eigenvalues are the
energy levels.

Energies are the same for a given l. Solutions are Geigenbauer functions

content from lecture by Leonard Susskind

6 | AQMLecture3.nb

If look at effective potential

0.2

2 4 6 8 10 12 r 14

-0.2

more than on bound energy level

characterised by number of nodes
-0.4

The more nodes the higher the angular momentum

content from lecture by Leonard Susskind

 AQMLecture3.nb | 7

1:01:00 Organise energy levels and state of atom

Each of the 2l + 1 mutliplets has a zero node as lowest energy state. Next Energy state has one
node, then next two nodes etc Levels for nodes aren’t necessarily evenly spaced

Energy levels for each l, lowest is node 0, next node 1 etc

Energy

0 1 2 3 l 4 5

Each l has own Schrodinger equation as it is a parameter in it

When energy gets too high escapes from orbit

Coulomb potential has a special feature that the zero node state for l=1 has the same energy as the
‘one’ node state for l=0 and simlarly higher nodes for l=1 line up with the node+1 for l=0

Special situation for Coulomb potential

....... ......... total 1+3+5+7+9=25

4
E
....... total 1+3+5+7=16
3

total 1+3+5=9
2

1 total 1+3=4

total 1
0
1 3 5 7 9 degeneracy for l

0
1 2 3 4
l
Seems like an extra degeneracy and is a symmetry but a rather bizarre one that is very specific to
the Coulomb potential

content from lecture by Leonard Susskind

8 | AQMLecture3.nb

Hydrogen approximately obeys this but is not an exact statement as corrections are necessary for
finite size of the nucleus, relativistic effects, spin etc

The finite size of the nucleus means we dont really have a point charge at the centre rather the
1
charge is distributed over the nucleus so that the potential is slightly different from
r

Note this is half the number for levels in the hydrogen atom of 2, 8, 18, 32 because haven’t
included spin

We set out to solve

 2
p
Hψ=Eψ with H = + V(r)
2m

∂2 ψ ∂2 ψ ∂2 ψ
-ℏ2 ( 2
+ 2
+ ) + V(r) ψ = E ψ
∂x ∂y ∂z2

Went to polar co-ordinates and used angular momentum eigenstates to deal with the angular part,
reducing the problem to a 1D Schrodinger equation.

When l=0 and no centrifugal barrier, classical would put the particle at rest at the centre, but quan-
tum mechanics prevents it sitting literally at the centre

Classically we moved the problem to the x-y plane; in quantum mechanics every wave fills up 3D so
we put the l(l + 1) to bring the 3D back

1.24:40 Harmonic Oscillator

Many things in nature approximate to the harmonic oscillator

Everything that has an equilibrium when disturbed a little is likely to behave like a harmonic oscillator

Consider weight on a spring

x = deviation from equilibrium

m = mass = 1
will set spring constant k=ω2

p2 kx
2
p2 ω 2 x2
So H = + = + (1)
2m 2 2 2

∂H  ∂H 
Check Hamilton’s equations of motion = x = -p
∂p ∂x

So doing differentials on (1)

∂H
= p is ok as we set m=1
∂p
∂H .. 
= ω2 x Acceleration = x = p = -ω2 x
∂x

We know classically HO swings back and forth with frequency ω

content from lecture by Leonard Susskind

 AQMLecture3.nb | 9

p2 ω 2 x2 1
H= + = ( p + iωx)( p - iωx) classical
2 2 2

But in QM x and p dont commute [x,p]= iℏ so need extra term, reminiscent of L x ± i Ly

1
H = (( p + iωx)( p - iωx) - iω[x,p])
2
1
= (( p + iωx)( p - iωx) - iω iℏ)
2
1 ωℏ
( p + iωx)( p - iωx) +
2 2

ωℏ
is a constant called the zero point energy, is there even when HO is in ground state
2

Classically there is no ground state energy as both x and p can be zero

Quantum mechanically cant have x and p both as zero

Note: x2 + p2 (ref Hamiltonian) is positive so cant have negative energy

ωℏ
Since is a constant we will drop it for now and just look at the
2
1
( p + iωx)( p - iωx) part to see what its spectrum and eigenvalues are
2

1 (p+iωx) (p-iωx)
( p + iωx)( p - iωx) = ω  standard way of working
2 2ω 2ω

Give these operators names, they will take us up and down the energy ladder

(p+iωx) (p-iωx)
a+ = a- =
2ω 2ω

Note: a+ is hermitian conjugate of a-

This gives: H = ωa+ a-

Look at commutation relations remembering [x,p]= iℏ

1
[a- ,a+ ] = [p-iωx, p+iωx] so looking at non-commuting parts
2ω
1 1
= [p, iωx] + [-iωx, p]
2ω 2ω

iω -iω
= - iℏ + iℏ
2ω 2ω
1 1
= ℏ + ℏ =ℏ
2 2

In units of ℏ
[a- ,a+ ] = 1

Define N=a+ a- so H=ωN

Note: N is Hermitian (because a+ is hermitian conjugate of a- ) and so has a complete set of eigen-
vectors

If we find these we will have the energy levels and eigenstates

content from lecture by Leonard Susskind

10 | AQMLecture3.nb

N|n>=n|n> we are not assuming the eigenvalue n to be an integer

Equivalently a+ a- |n>=n|n>

since (a- a+ - a+ a- ) = 1

(a- a+ - a+ a- ) |n> = |n>

want to show a+ is a raising operator

a+ (a- a+ - a+ a- ) |n> = a+ |n>

a+ a- a+ |n> - a+ a+ a- |n> = a+ |n>

a+ a- a+ |n> - a+ n |n> = a+ |n>

Na+ |n>= a+ (n + 1) |n>

Na+ |n>= (n + 1)a+ |n>

So raising operator a+ gives new eigenvector/state of N with eigenvalue one unit up

Can continue up finding more eigenstates with eigenvalues +1 above the previous one

Gives higher and higher energies since E = ωn

Similarly a- takes us down through n but must stop eventually as cant go negative, so

a- |n>= n |n-1 > or a- |n>=0 so n are integers

a+ |n>= n + 1 |n+1 >

ωℏ
Putting the constant that we dropped earlier and ℏ back in
2

Spectrum of N is for n starting and 0

ωℏ
ωℏn +
2

with n as an integer starting from 0

Next lecture will use this to solve some problems

content from lecture by Leonard Susskind