Quantum Mechanics Review Sheet

Michael Li
May 5, 2016

Physical background
Photoelectric effect. Electrons in atoms and line spectra. Particle diffraction. [1]

Schrödinger equation and solutions

De Broglie waves. Schrödinger equation. Superposition principle. Probability interpretation,
density and current. [2]
Stationary states. Free particle, Gaussian wave packet. Motion in 1-dimensional potentials,
parity. Potential step, square well and barrier. Harmonic oscillator. [4]

Observables and expectation values

Position and momentum operators and expectation values. Canonical commutation relations.
Uncertainty principle. [2]
Observables and Hermitian operators. Eigenvalues and eigenfunctions. Formula for expecta-
tion value. [2]

Hydrogen atom
Spherically symmetric wave functions for spherical well and hydrogen atom.
Orbital angular momentum operators. General solution of hydrogen atom. [5]

1
Contents

Contents 2

1 Schrödinger Equation and Wavefunctions 3

2 One Dimensional Examples 4

2.1 Parity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3 Examples 4

4 Expectation and Uncertainty 8

4.1 Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.2 Ehrenfest’s Theorem and the Uncertainty Principle . . . . . . . . . . 9

5 More One Dimension Results 10

5.1 Gaussian Wavepackets . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.2 Scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5.3 Bound vs Scattering States . . . . . . . . . . . . . . . . . . . . . . . . 14

6 Axioms for Quantum Mechanics 15

7 Quantum Mechanics. Now in 3DTM 16

7.1 Angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
7.2 Spherical Polars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

8 The Hydrogen Atom 19

8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
8.2 General solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

2
1 Schrödinger Equation and Wavefunctions
Biggest difference between classical and quantum physics: You can’t be sure of any-
thing at any time. Everything is formulated in probability. The probability of a par-
Rb
ticle being in [a, b] is a |ψ(x)|2 dx, where ψ(x) is its wavefunction. Here is a non-
exhaustive list of basic principles that are good to know:
- To calculate the probability, we need to normalize the wavefunctions so that
the square of it is actually a probability distribution. But we wouldn’t do it
otherwise because it just involves fiddling with constants. However, we would
like to work for normalizable wavefunctions, or those that satisfy:
Z ∞
|ψ(x)|2 dx < ∞.
−∞

Because if they don’t, we are in normalization trouble.

- Equations in quantum mechanics are linear, so any linear combination of solu-
tions is a solution.
- In quantum Mechanics, we conduct everything in operators that operate on the
wavefunction, which contain all the information. Important ones are:

position x̂ = x x̂ψ = xψ(x)

momentum p̂ = −i~ ∂x ∂
p̂ψ = −i~ψ 0 (x)
2
p̂ ∂2
energy H = 2m + V (x̂) Hψ = −~2 ∂x 2 ψ + V (x)ψ(x)

- An observable corresponding to an operator is definite if and only if it is an

eigenvalue of the operator. For example, the particle has energy E is and only
if Hψ = Eψ. Otherwise, it follows a probability distribution.
Now we introduce the time independent/dependent Schrödinger equation:
Definition (Schrödinger equation). The time-independent Schrödinger equation (T-ID
SE) is the energy eigenvalue equation
~2 00
Hψ = Eψ ⇔ − ψ + V (x)ψ = Eψ.
2m
The time-dependent Schrödinger equation (T-D SE) is:
∂Ψ ∂Ψ ~2 ∂ 2 Ψ
i~ = HΨ ⇔ i~ =− + V (x, t)Ψ
∂t ∂t 2m ∂x2
Where we have written the wavefunction as Ψ.
Then we can use separation technique to find a special class of time-dependent
wavefunctions, namely Ψ(x, t) = ψ(x)T (t) where ψ(x) satisfy the T-ID SE, which
are called stationary states:
Definition (Stationary state). A stationary state is a state of the form
 
iEt
Ψ(x, t) = ψ(x) exp − .
~
where ψ(x) is an eigenfunction of the Hamiltonian with eigenvalue E. This term is
also sometimes applied to ψ instead.

3
 We have the following proposition:
Proposition. The probability density P (x, t) = |Ψ(x, t)|2 obeys
∂P ∂j
=− ,
∂t ∂x
 ∗

i~
where j(x, t) = − 2m Ψ∗ dΨ
dx − dΨ
dx Ψ is the probability current.

Proof.
∂P ∂Ψ ∂Ψ∗ i~ 00 i~ 00∗ ∂j
= Ψ∗ + Ψ = Ψ∗ Ψ − Ψ Ψ=− .
∂t ∂t ∂t 2m 2m ∂x

Note that this is expressed in a space derivative, so the change in probability of

finding the particle in [a, b] is just j(a, t) − j(b, t), or the current entering at a and
leaving at b.

2 One Dimensional Examples

Before we enter examples, we first illustrate a concept:

2.1 Parity
Consider the Schrödinger equation for a particle of mass m

~2 00
Hψ = − ψ + V (x)ψ = Eψ.
2m
with potential V (x) = V (−x). By changing variables x → −x, we see that ψ(x) is
an eigenfunction of H with energy E if and only if ψ(−x) is an eigenfunction of H
with energy E. There are two possibilities:
(i) If ψ(x) and ψ(−x) is the same quantum state, this can only happen if ψ(−x) =
ηψ(x) for some constant η. Then we get that η = ±1 and ψ(−x) = ±ψ(x).
We call η the parity, and say ψ has even/odd parity if η is +1/ − 1 respectively.
(ii) If ψ(x) and ψ(−x) are different quantum states, then we take linear combi-
nations ψ± (x) = α(ψ(x) ± ψ(−x)), and these are eigenstates with energy
eigenvalue E, where α is for normalization. Then by construction, ψ± (−x) =
±ψ± (x) and have parity η = ±1.
Hence, if we are given a potential with reflective symmetry V (−x) = V (x), then we
can restrict our attention and just look for solutions with ±1 parity. Now we go for
examples.

3 Examples
Infinite Well The simplest case to consider is the infinite well. Here the potential is infinite
outside the region [−a, a], so for |x| > a, we must have ψ(x) = 0, or else
V (x)ψ(x) would be infinite.

4
 V

x
−a a

We require ψ = 0 for |x| > a and ψ continuous at x = ±a. Within |x| < a,
the Schrödinger equation is

~2 00
− ψ = Eψ.
2m
We simplify this to become

ψ 00 + k 2 ψ = 0,
2 2
k
where E = ~2m . Here, instead of working with the complex exponentials, we
use sin and cos since we know well when these vanish. The general solution is
thus
ψ = A cos kx + B sin kx.
Now we solve for the boundary conditions, so that ψ vanishes at ±a. This turns
out to give
~2 π 2 2
En = n ,
8ma2
where n = 1, 2, · · · , and the wavefunctions are
  12 (
1 cos nπx
2a n odd
ψn (x) = .
a sin nπx
2a n even

If you stare at this long enough, you can realize they are just standing waves.

Potential Well We consider a potential:

V
x

a −U
−a

The potential is given by some constant U > 0. We want to seek energy levels
for a particle of mass m, defined by the Schrödinger equation

~2 00
Hψ = − ψ + V (x)ψ = Eψ.
2m
For energies in the range −U < E < 0, we set

~2 k 2 ~2 κ2
U +E = > 0, E=− ,
2m 2m

5
where k, κ > 0 are new real constants. Note they must satisfy
2mU
k 2 + κ2 = .
~2
Using these constants, the Schrödinger equation becomes
(
ψ 00 + k 2 ψ = 0 |x| < a
ψ 00 − κ2 ψ = 0 |x| > a.

We first consider the even parity solutions ψ(−x) = ψ(x). We can write our
solution as (
A cos kx |x| < a
ψ=
Be−κ|x| |x| > a
We now match ψ and ψ 0 at x = a to make it continuous. So we need
A cos ka = Be−κa
−Ak sin ka = −κBe−κa .
By parity, there is no additional information from x = −a. We can divide the
equations to obtain
k tan ka = κ.
this is still not something we can solve easily. To find when solutions exist, it
is convenient to introduce
ξ = ka, η = κa,
Hence the solution we need are solutions to
2ma2 U
η = ξ tan ξ. and ξ 2 + η 2 = .
~2
Where the second equation comes from our initial relation. We can look for
solutions by plotting these two equations.

So there will be a different number of solutions depending on the value of

2ma2 U/~2 . In particular, if
1/2
2mU a2

(n − 1)π < < nπ,
~2
then we have exactly n even parity solutions (for n ≥ 1). If E > 0 or E < −U ,
we have non-normalizable solutions.
The odd parity case, not shown here, can be done similarly. It can be shown that
2
there are no bound states (normalizable energy eigenfunctions) if a2 U < (πh)
8m .

6
 V

x
Harmonic Oscillator
This is a harmonic oscillator of mass m with
1
V (x) = mω 2 x2 .
2
Note the similarity with this to the second term in a taylor expansion. And
assuming x0 is an equilibrium, the first term is zero so this is the first non-
zero approximation term! That’s why people say physics is just increasingly
complicated harmonic oscillators.
We seek all normalizable solutions to to the time-independent Schrödinger equa-
tion
~2 00 1
Hψ = − ψ + mω 2 x2 ψ = Eψ.
2m 2

12
So simplify constants, we define y = mω ~ x and E = 2E
~ω both of which is
dimensionless. Then we are left with
d2 ψ
− + y 2 ψ = Eψ.
dy 2
Now we try
1 2
ψ = f (y)e− 2 y .
Why? Well, we want to offset the y 2 factor in the differential equation here.
Then the Schrödinger equation gives

d2 f df
2
− 2y + (E − 1) = 0.
dy dy

ar y r ,
P
This is known as Hermite’s equation. We try a series solution f (y) = r≥0
and substitute in to get
X
(r + 2)(r + 1)an+2 + (E − 1 − 2r)ar y r = 0.

r≥0

This holds if and only if

2r + 1 − E
ar+2 = ar , r ≥ 0.
(r + 2)(r + 1)

We have independent in a0 and a1 so they give 2 solutions. But we want nor-

malizable solutions. We can observe that the coefficients obey:
1
ap /ap−2 ∼ .
p

7
 2
So we are getting something like a series expansion of ey , which is bad, as ψ
would not be normalizable. So we need to terminate the series. This occurs iff
E = 2n + 1 for some n. Note that for each n, only one of the two independent
solutions is normalizable. So for each E, we get exactly one solution.
For n even, we have
2r − 2n
ar+2 = ar
(r + 2)(r + 1)
for r even, and ar = 0 for r odd, and the other way round when n is odd.
The solutions are thus f (y) = hn (y), where hn is a polynomial of degree n
with hn (−y) = (−1)n hn (y). For example, we have

h1 (y) = a1 y h2 (y) = a0 (1 − 2y 2 )

With constants fixed by normalization. These are known as the Hermite poly-
nomials. Thus, we have:  
1
En = ~ω n + ,
2
for n = 0, 1, 2, · · · .
The wavefunctions are
mω  12
   
1 mω 2
ψn (x) = hn x exp − x ,
~ 2 ~

4 Expectation and Uncertainty

This is the section for theory behind quantum mechanics. Wait. Didn’t we just solve
like the Schrödinger equations? Well, we did… But there is much more.

4.1 Definitions
First up, notations and some definitions:
Definition (Inner product). Let ψ(x) and φ(x) be normalizable wavefunctions at
some fixed time. We define the complex inner product by
Z ∞
(φ, ψ) = φ(x)∗ ψ(x) dx.
−∞

Definition (Norm). The norm of a wavefunction ψ, written, kψk is defined by

Z ∞
kψk2 = (ψ, ψ) = |ψ(x)|2 dx.
−∞

Definition (Expectation value). The expectation value of any observable H on the

state ψ is
hHiψ = (ψ, Hψ).

8
Definition (Uncertainty, or Variance). The uncertainty in position (∆x)ψ and mo-
mentum (∆p)ψ are defined by
(∆x)2ψ = h(x̂ − hx̂iψ )2 iψ = hx̂2 iψ − hx̂i2ψ ,
with exactly the same expression for momentum:
(∆p)2ψ = h(p̂ − hp̂iψ )2 iψ = hp̂2 iψ − hp̂i2ψ ,
Definition (Hermitian operator). An operator Q is Hermitian iff for all normalizable
φ, ψ, we have
Z Z
(φ, Qψ) = (Qφ, ψ) ⇔ φ∗ Qψ dx = (Qφ)∗ ψ dx.

x̂, p̂ and H are all Hermitian (From definition, just use integration by parts).

4.2 Ehrenfest’s Theorem and the Uncertainty Principle

The two theorems are to show you that quantum mechanics is kind of similar (Ehren-
fest) to classical mechanics, but not really (Uncertainty Principle).
Theorem (Ehrenfest’s theorem).
d 1
hx̂iΨ = hp̂iΨ
dt m
d
hp̂iΨ = −hV 0 (x̂)iΨ .
dt
Proof. We have
d
hx̂iΨ = (Ψ̇, x̂Ψ) + (Ψ, x̂Ψ̇)
dt      
1 1
= HΨ, x̂Ψ + Ψ, x̂ H Ψ
i~ i~

Since H is Hermitian, we can move it around and get

1 1 1
=− (Ψ, H(x̂Ψ)) + (Ψ, x̂(HΨ)) = (Ψ, (x̂H − H x̂)Ψ).
i~ i~ i~
But we know
~2 ~2 i~
x̂H − H x̂Ψ = − (xΨ00 − (xΨ)00 ) + (xV Ψ − V xΨ) = − Ψ0 = p̂Ψ.
2m m m
So done.The second part is similar. So we have:
d 1
hp̂iΨ = (Ψ̇, p̂Ψ) + (Ψ, p̂Ψ̇) = (Ψ, (p̂H − H p̂)Ψ)
dt i~
Then of course, we have
−~2
 
(p̂H − H p̂)Ψ = −i~ ((Ψ00 )0 − (Ψ0 )00 ) − i~((V (x)Ψ)0 − V (x)Ψ0 )
2m
= −i~V 0 (x)Ψ.
So done.

9
Theorem (Heisenberg’s uncertainty principle). If ψ is any normalized state (at any
fixed time), then
~
(∆x)ψ (∆p)ψ ≥ .
2
Yes, this is the famed theorem that we cannot know anything exactly. To prove
this we need the following:
Definition (Commutator). Let Q and S be operators. Then the commutator is de-
noted and defined by
[Q, S] = QS − SQ.
This is a measure of the lack of commutativity of the two operators.
In particular, the commutator of position and momentum is
[x̂, p̂] = x̂p̂ − p̂x̂ = i~.
Now we prove the Uncertainty principle:
Proof. Choose α = hx̂iψ and β = hp̂iψ , and define
X = x̂ − α, P = p̂ − β.
Then we have
(∆x)2ψ = (ψ, X 2 ψ) = (Xψ, Xψ) = kXψk2
(∆p)2ψ = (ψ, P 2 ψ) = (P ψ, P ψ) = kP ψk2
Then we have
(∆x)ψ (∆p)ψ = kXψkkP ψk
≥ |(Xψ , PΨ )|
≥ | Im(Xψ , PΨ )|
 h i
1
≥ (Xψ, P ψ) − (P ψ, Xψ) 
2i
 h i  1   
1  ~  ~
= (ψ, XP ψ) − (ψ, P Xψ)  =  (ψ, [X, P ]ψ) =  (ψ, ψ) = .
   
2i 2i 2 2

5 More One Dimension Results

5.1 Gaussian Wavepackets
A wavepacket is some wavefunction that is localized in space, but this is really not
well defined. But we do have a good definition of this:
Definition (Gaussian wavepacket). A Gaussian wavepacket is given by
 α 1/4 1 2
Ψ0 (x, t) = 1/2
e−x /2γ(t) ,
π γ(t)
for some γ(t).
Now we will use these functions later. First, we have:

10
5.2 Scattering
Consider the time-dependent Schrödinger equation with a potential barrier. We send
a wavepacket to a barrier, and in quantum mechanics, we would expect some part to
pass it, and some part to be reflected:

AΨref BΨtr

Here Ψ, Ψref and Ψtr are normalized wavefunctions, and

Pref = |A|2 , Ptr = |B|2 .
are the probabilities of reflection and transmission respectively.
Now generally these are hard problems, but we can use the following trick: We
allow Ψ(x, t) to represent beams of infinitely many particles, with |Ψ(x, t)|2 being the
density of the number of particles (per unit length) at x, t. When we do this, instead
of having one particle and watching it evolve, we constantly send in particles so that
the system does not appear to change with time. This allows us to find steady states.
Therefore, to determine, say, the probability of reflection, we kind of just look at the
proportion of particles moving left compared to the proportion of particles moving
right in this steady state.
For these particle beams, Ψ(x, t) is bounded, but no longer normalizable. Recall
that for a single particle, the probability current was defined as
i~
j(x, t) = − (Ψ∗ Ψ0 − ΨΨ0∗ ).
2m
If we have a particle beam instead of a particle, and Ψ is the particle density instead
of the probability distribution, j now represents the flux of particles at x, t, ie. the
number of particles passing the point x in unit time.
Often, when solving a scattering problem, the solution will involve sums of mo-
mentum eigenstates. So it helps to understand these better. Our momentum eigen-
states are
ψ(x) = Ceikx ,
which are solutions to the time-independent Schrödinger equation with V = 0 with
2 2
k
E = ~2m .
Applying the momentum operator, we find that p = ~k is the momentum of each
particle in the beam, and |ψ(x)|2 = |C|2 is the density of particles in the beam. We
can also evaluate the current to be
~k 2
j= |C| .
m
p 2
This makes sense. ~k m = m is the velocity of the particles, and |C| is how many
particles we have. So this still roughly corresponds to what we used to have classically.
In scattering problems, we will seek the transmitted and reflected flux jtr , jref in
terms of the incident flux jinc , and the probabilities for transmission and reflection
are then given by
|jtr | |jref |
Ptr = , Pref = .
|jinc | |jinc |
Now we would illustrate this using two examples:

11
Potential Step We consider a wavepacket going into this:

V (x)

E < U We apply the standard method, introducing constants k, κ > 0 such that

~2 k 2 ~2 κ2
E= , U −E = .
2m 2m
Then the Schrödinger equation becomes
(
ψ 00 + k 2 ψ = 0 x < 0
ψ 00 − κ2 ψ = 0 x > 0

The solutions are ψ = Ieikx + Re−ikx for x < 0, and ψ = Ce−κx for
x > 0 (since ψ has to be bounded).
Since ψ and ψ 0 are continuous at x = 0, we have the equations
(
I +R=C
.
ikI − ikR = −κC

So we have
k − iκ 2k
R= I, C= I.
k + iκ k + iκ
If x < 0, ψ(x) is a superposition of beams (momentum eigenstates) with
|I|2 particles per unit length in the incident part, and |R|2 particles per
unit length in the reflected part, with p = ±~k. The current is

~k ~k
j = jinc + jref = |I|2 − |R|2 ,
m m
The probability of reflection is

|jref | |R|2
Pref = = = 1,
|jinc | |I|2

On the right hand side, we have j = 0. So Ptr = 0.

E > U This is really similar, except we have

~2 k 2 ~2 κ2
E= , E−U = ,
2m 2m
We then match the two solutions again (skipping some steps to show you
the important part): (
I +R=T
ikI − ikR = ikT.

12
 We can solve these to obtain
k−κ 2k
R= I, T = I.
k+κ k+κ
Our flux on the left is now
~k ~k
j = jinc + jref = |I|2 − |R|2 ,
m m
while the flux on the right is
~κ
j = jtr |T |2 .
m
The probability of reflection and transmission is
2
|R|2 |T |2 κ

|jref | k−κ |jtr | 4kκ
Pref = = 2
= , Ptr = = 2
= .
|jinc | |I| k+κ |jinc | |I| k (k + κ)2

Potential Barrier Consider the following potential:

x
0 a

Now consider a stationary state with energy E with 0 < E < U . We set the
constants
~2 k 2 ~2 κ2
E= , U −E = .
2m 2m
Then the Schrödinger equations become

ψ 00 + k 2 ψ = 0 x<0
00 2
ψ −κ ψ =0 0<x<a
00 2
ψ +k ψ =0 x>a

So we get

ψ = Ieikx + Re−ikx x<0

κx −κx
ψ = Ae + Be 0<x<a
ψ = T eikx x>a

Matching ψ and ψ 0 at x = 0 and a gives the equations

I +R=A+B
ik(I − R) = κ(A − B)
Ae κa
+ Be−κa = T eika
κ(Aeκa − Be−κa ) = ikT eika .

13
 We can work out the boring algebra to obtain:
−1
k 2 − κ2

−ika
T = Ie cosh κa − i sinh κa
2kκ

Therefore we can use these to find the transmission probability, and it turns out
to be −1
|T |2 U2

|jtrj | 2
Ptr = = = 1 + sinh κa .
|jinc | |I|2 4E(U − E)
This demonstrates quantum tunneling. There is a non-zero probability that the
particles can pass through the potential barrier even though it classically does
not have enough energy.

5.3 Bound vs Scattering States

As |x| → ∞ the T-ID SE gives:

~2 00
− ψ = Eψ.
2m
Which give solutions like:
( 2 2
Aeikx + Be−ikx k
E = ~2m >0
ψ∼ ~2 κ 2
Aeκx + Be−κx E = − 2m < 0.

For it to be bound, we need E < 0. Thus we need to have

(
Aeκx x → −∞
ψ∼ −κx
Be x → +∞

Which is overdetermined. That’s why bound state energy levels are quantized.
If it is not bounded, then we have:
(
Ieikx + Re−ikx x → −∞
ψ∼
T eikx x → +∞

So we have:
|jref |
Pref = |Aref |2 =
|jinc |
|jtr |
Ptr = |Atr |2 = ,
|jinc |
R T
where Aref (k) = I and Atr (k) = I .
Note. In quantum mechanics, Amplitude squared generally gives probability.

14
6 Axioms for Quantum Mechanics
Note. This section is in the notes but honestly I fail to see how they can test this. But
still read through it. It will help a lot when (if) you do PQM next year.
Now we would list the axioms, and some useful results:

- States of a quantum system correspond to non-zero elements of a complex vec-

tor space V (which has nothing to do with the potential), with ψ and αψ phys-
ically equivalent for all α ∈ C \ {0}.
- There is also a complex inner product on V .

- A measurable quantity, named observable is a Hermitian operator.

- A Hermitian operator has orthogonal eigenvectors with respect to different
eigenvalues, and the eigenvalues of it are real. (cf. Vectors and Matrices)
- Any state can be written as a (maybe infinite) linear combination of eigenstates
of Q. We sat the set of eigenstates is complete. We would not prove this.
P
- Let a state be written as ψ = n αn χn . Then
◦ The outcome of a measurement is some eigenvalue of Q.
◦ The probability of having λn is |αn |2 .
◦ The measurement forces the state into χn and is instantaneous.
Note. The last one is really because measuring it means knowing it at a
certain state, and in some given small period of time, you can’t let it be
very far away from the state you just measured.
- Now the expectation and uncertainty of Q in state ψ can be reformulated to be:
X
hQiψ = (ψ, Qψ) = λn Pn
X
(∆Q)2ψ = h(Q − hQiψ )2 iψ = hQ2 iψ − hQi2ψ = (λn − hQiψ )2 Pn
n

- The state of a quantum system Ψ(t) obeys the Schrödinger equation

i~Ψ̇ = HΨ,

where H is a Hermitian operator, the Hamiltonian; this holds at all times except
at the instant a measurement is made. This is called the wavefunction collapse.
Why? Well………You just asked a million dollar question.
- For any observable Q, the number of linearly independent eigenstates with
eigenvalue λ is the degeneracy of the eigenvalue. In other words, the degen-
eracy is the dimension of the eigenspace

Vλ = {ψ : Qψ = λψ}.

An eigenvalue is non-degenerate if the degeneracy is exactly 1, and is degenerate

if the degeneracy is more than 1.

15
Not an Axiom What if we wanted to distinguish degenerate states? Then we need two observ-
ables A and B, and the state needs to be an eigenstate for both of them. From
linear algebra, we can know that this is possible if A and B commutes.

Not an Axiom
Theorem (Ehrenfest’s theorem in General). If Q is any operator with no ex-
plicit time dependence, then

d
i~ hQiΨ = h[Q, H]iΨ ,
dt
where [Q, H] = QH − HQ is the commutator. The proof is done by expanding
out the definition and replacing −i~Ψ̇ with HΨ.
P
Not an Axiom For a state at time 0 written as Ψ(0) = n αn ψn , then using stationary states,
we can write the general form as:
X
Ψ(t) = αn e−iEn t/~ ψn .
n

7 Quantum Mechanics. Now in 3DTM

Now we go into 3D. Everything we have learned pretty much just follows directly,
and commutator relations such as [x̂i , p̂j ] = −i~δij , [x̂i , x̂j ] = [p̂i , p̂j ] = 0 don’t
really change except that indices are added. Now we define the following:

Definition (Structureless particle). A structureless particle is one for which all ob-
servables can be written in terms of position and momentum.
In reality, this is mostly not true but we don’t care. The method of solving this is
simply by separation of variables where we look for solutions in one dimension and
multiply them together. I know. It is not exciting. Let’s get to the more exciting stuff:

7.1 Angular momentum

This is the important stuff.

Definition (Angular momentum). The angular momentum is a vector of operators

L = x̂ ∧ p̂ = −i~x ∧ ∇.

In components, this is given by

∂
Li = εijk x̂j p̂k = −i~εijk xj .
∂xk
For example, we have
 
∂ ∂
L3 = x̂1 p̂2 − x̂2 p̂1 = −i~ x1 − x2 .
∂x2 ∂x1

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Definition. The total angular momentum operator is

L2 = Li Li = L21 + L22 + L33 .

Of course, everything defined above is Hermitian and thus an observable. We have

the following commutator relations:

[Li , Lj ] = i~εijk Lk [Li , x̂j ] = i~εijk x̂k , [Li , p̂j ] = i~εijk p̂k

And also the following:

[L2 , Li ] = 0
All of this can be proven easily using indices operations. Now we introduce a lemma
that comes in handy:
Lemma (Leibnitz’s Property). We have, for any three operators A, B, C:

[AB, C] = [A, C]B + A[B, C] [A, BC] = [A, B]C + B[A, C]

This lemma allows us to deal with products effectively. Very. Effectively.

7.2 Spherical Polars

Now we can rewrite the angular momentum in spherical polars. The formula for L3
will be rather simple, since x3 is our axis of rotation. However, those for L1 and L2
will be much more complicated. Instead of writing them out directly, we instead write
down the formula for L± = L1 ± iL2 . A routine application of the chain rule gives

∂
L3 = −i~
∂φ
 
∂±iϕ ∂
L± = L1 ± iL2 = ±~e ± i cot θ
∂θ ∂φ
1 ∂2
   
2 2 1 ∂ ∂
L = −~ sin θ + .
sin θ ∂θ ∂θ sin2 θ ∂φ2

From above, we can see that we can measure L3 and L2 simultaneously, so there
are simultaneous eigenfunctions of these operators, which we call Y`m (θ, ϕ), with
` = 0, 1, 2, · · · and m = 0, ±1, ±2, · · · , ±`. These have eigenvalues ~m for L3 and
~2 `(` + 1) for L2 .
In spherical polars, we have:

~2 1 ∂ 2 1 1 2
H=− 2
r+ L + V (r).
2µ r ∂r 2µ r2
We can check that
[Li , H] = [L2 , H] = 0.
This implies we can use the eigenvalues of H, L2 and L3 to label our solutions to the
equation. Therefore, we can simultaneously measure them, so the joint eigenstates
must be:
ψ(x) = R(r)Y`m (θ, ϕ),

17
Now we then try to solve the Schrodinger equation, which gives:

~2 1 d2 ~2
− 2
(rR) + `(` + 1)R + V R = ER.
2µ r dr 2µr2
Now R(r) is called the radial part of the wavefunction, and we will work with χ(r) =
rR(r), often called the radial wavefunction. Then the equation turns into:

~2 00 ~2 `(` + 1)
− χ + χ + V χ = Eχ.
2µ 2µr2
The radial Schrödinger Equation. NOw since we would like R to be finite as r → 0, so
χ = 0 at r = 0. The normalization conditions turns into:
Z ∞
|R(r)|2 r2 dr < ∞.
0

Alternatively, this requires

Z ∞
|χ(r)|2 d r < ∞.
0

Now we look at an example:

Example (Three-dimensional well). We now plot our potential as a function of r:

V
a
r

−U

We now look for bound state solutions to the Schrödinger equation with −U < E <
0, with total angular momentum quantum number `.
For r < a, our radial wavefunction χ obeys

`(` + 1)
χ00 − χ + k 2 χ = 0,
r2
where k is a new constant obeying

~2 k 2
U +E = .
2µ
For r ≥ a, we have
`(` + 1)
χ00 − χ − κ2 χ = 0,
r2
with κ obeying
~2 κ2
E=− .
2µ
We can solve in each region and match χ, χ0 at r = a, with boundary condition
χ(0) = 0. Note that given this boundary condition, solving this is equivalent to
solving it for the whole R but requiring the solution to be odd.

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 Solving this for general ` is slightly complicated (would be taught in Applied
Quantum Mechanics course). So we shall look at some particular examples.
For ` = 0, we have no angular term, and we have done this before. The general
solution is (
A sin kr r < a
χ(r) =
Be−κr r>a
Matching the values at x = a determines the values of k, κ and hence E.
For ` = 1, it turns out the solution is just
(
1


A cos kr − kr sin kr r < a
χ(r) = 1

−κr .
B 1 + kr e r>a

After matching, the solution is

χ(r)
ψ(r) = R(r)Y1m (θ, ϕ) = Y1m (θ, ϕ),
r
where m can take values m = 0, ±1.

8 The Hydrogen Atom

After developing so much theory, we now have the tools to describe…..the Hydrogen
Atom! Isn’t that exciting?
Note. Note we are not going to actually solve this, because electrons have spin, so
they behave slightly more weirdly. Although this doesn’t really affect the hydrogen
atom, it does add complexity to the equations. See PQM for the actual solution.

8.1 Introduction
Consider an electron moving in a Coulomb potential

e2 1
V (r) = − .
4πε0 r
This potential is due to a proton stationary at r = 0. We follow results from the last
section of the last chapter, and set the mass µ = me , the electron mass. The joint
energy eigenstates of H, L2 and L3 are of the form

φ(x) = R(r)Y`m (θ, ϕ)

for ` = 0, 1, · · · and m = 0, ±1, · · · , ±m.

The radial part of the Schrödinger equation can be written
2 `(` + 1) 2λ
R00 + R0 − R+ R = κ2 R, (∗)
r r2 r
with
m2 −~2 κ2
λ= , E = .
4πε0 ~2 2me
Note that here we work directly with R instead of χ, as this turns out to be easier
later on.

19
 The goal of this chapter is to understand all the (normalizable) solutions to this
equation (∗).
Now we start by guessing. For large r, we get

R00 ∼ κ2 R.

This implies R ∼ e−κr for large R.

For small r, we by assumption know that R is finite, while R0 and R00 could po-
tentially go crazy. So we multiply by r2 and discard the rR and r2 R terms to get

r2 R00 + 2rR0 − `(` + 1)R ∼ 0.

This gives the solution R ∼ r` .

We’ll be bold and try a solution of the form

R(r) = Cr` e−κr .

When we substitute this in, we will get three kinds of terms. The r` e−κr terms match,
and so do the terms of the form r`−2 e−κr . Finally, we see the r`−1 e−κe terms match
if and only if

2(`r`−1 )(−κe−κr ) + 2(r`−1 )(−κe−κr ) + 2λr`−1 e−κe = 0.

When we simplify this mess, we see this holds if and only if

(` + 1)κ = λ.

Hence, for any integer n = ` + 1 = 1, 2, 3, · · · , there are bound states with energies
2
~2 λ2 e2

1 1
En = − = − me .
2me n2 2 4πε0 ~ n2

In our model, the total angular momentum eigenvalue is thus

~2 `(` + 1) = ~2 n(n − 1),

But this is only one solution as for each energy level, there are many possible
angular momentums.

8.2 General solution

We guessed our solution r` e−κr above by looking at the asymptotic behaviour at large
and small r. We then managed to show that this is one solution of the hydrogen atom.
But we want all of them. So we continue guessing:

R(r) = e−κr f (r).

Putting it in, we obtain

 
2 `(` + 1) f
f 00 + f 0 − f = 2 κf 0
+ (κ − λ) .
r r2 r

20
Now each side of the equality is equidimensional, which is great for series solutions.
This equation is regular singular at r = 0, so we guess a solution of the form
∞
X
f (r) = ap rp+σ , a0 6= 0.
p=0

Then substitution gives

X X
((p + σ)(p + σ − 1) − `(` + 1))ap rp+σ−2 = 2(κ(p + σ + 1) − λ)ap rp+σ−1 .
p≥0 p≥0

The lowest term gives us the indicial equation

σ(σ + 1) − `(` + 1) = (σ − `)(σ + ` + 1) = 0.

So either σ = ` or σ = −(` + 1). We discard the σ = −(` + 1) solution since this

would make f and hence R singular at r = 0. So we have σ = `.
Given this, the coefficients are then determined by
2(κ(p + `) − λ)
ap = ap−1 , p ≥ 1.
p(p + 2` + 1)
Similar to the harmonic oscillator, we now observe that, unless the series terminates,
we have
ap 2κ
∼
ap−1 p
as p → ∞, which matches the behaviour of rα e2κr (for some α). So R(r) is normal-
izable only if the series terminates. Hence the possible values of λ are

κn = λ

for some n ≥ ` + 1. So the resulting energy levels are exactly those we found before:
2
~2 2 ~2 λ2 e2

1 1
En = − κ =− = − me .
2me 2me n2 2 4πε0 ~ n2
for n = 1, 2, 3, · · · . This n is called the principle quantum number.
For any given n, the possible angular momentum quantum numbers are

` = 0, 1, 2, 3, · · · , n − 1
m = 0, ±1, ±2, · · · , ±`.

The simultaneous eigenstates are then

ψn`m (x) = Rn` (r)Y`m (θ, ϕ),

with
Rn`r = r` gn` (r)e−λr/n ,
where gn` (r) are (proportional to) the associated Lagnerre polynomials.
In general, the “shape” of probability distribution for any electron state depends on
r and θ, ϕ mostly through Y`m . For ` = 0, we have a spherically symmetric solutions

ψn00 (x) = gn0 (r)e−λr/n .

21
 The degeneracy of each energy level En is
n−1
X `
X n−1
X
1= (2` + 1) = n2 .
`=0 m=−` `=0

So. We solved the hydrogen atom. Kind of. By guessing. But hey, we solved it.

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