Quantum Mechanics

Week 3

Mark Benazet Castells

March 06, 2024
Quantum Mechanics

Exercise Material

Webpage

Mark Benazet Castells | ETH Zürich 2/31

Week 3

Recap

Review

Clicker Questions

Exercises
Quantum Mechanics

Review of Last Week

• Any questions on last week’s topics?

• Feedback on the previous session?

• Additional materials you’d like to get?

Mark Benazet Castells | ETH Zürich 4/31

Quantum Mechanics

Recap
Time-Dependent Schrödinger Equation (TDSE)

∂Ψ(x, t) ~2 ∂ 2 Ψ(x, t)
i~ =− + V (x, t)Ψ(x, t)
∂t 2m ∂x2

Normalization

Z ∞
!
|C · Ψ(x, t)|2 dx = 1
−∞

Mark Benazet Castells | ETH Zürich 5/31

Quantum Mechanics

Measurements

Observable Z ∞
z }| {
h Q(x, p) i = Ψ∗ · Q̂(x̂, p̂) ·Ψdx
| {z } −∞ | {z }
Expectation Value Operator

Uncertainty Principle

~
σx · σp ≥
2

Mark Benazet Castells | ETH Zürich 6/31

Separation of Variables

Review
Separation of Variables
We rewrite the Time-Dependent Schrödinger Equation (T.D.S.E.) and
V (x, t) → V (x):

!
∂ ~2 ∂ 2
i~ Ψ(x, t) = − + V (x) Ψ(x, t)
∂t 2m ∂x2

Mark Benazet Castells | ETH Zürich 7/31

Separation of Variables

Derivation of Separable Variables:

Assuming Ψ(x, t) = ψ(x) · ϕ(t), we substitute to obtain:

∂ϕ(t) ~2 ∂ 2 ψ(x)
i~ψ(x) =− ϕ(t) + V (x)ψ(x)ϕ(t)
∂t 2m ∂x2

Separating variables yields:

1 ∂ϕ(t) ~2 1 ∂ 2 ψ(x)
i~ =− + V (x) = E
ϕ(t) ∂t 2m ψ(x) ∂x2
| {z } | {z }
LHS RHS

Because each side depends on a different variable, they must equal a

constant, E, the separation constant

Mark Benazet Castells | ETH Zürich 8/31

Separation of Variables

LHS RHS (T.I.S.E.)

1 ∂ϕ
i~ =E
ϕ ∂t ~2 1 ∂ 2 ψ
− +V =E
Z
∂ϕ E
Z 2m ψ ∂x2
= ∂t
ϕ i~
E ~2 ∂ 2 ψ
ln ϕ = t + C1 − + V ψ = Eψ
i~ 2m ∂x2
1
With C2 = eC1 and i = −i, 2
~ ∂
With Ĥ = − 2m
2
+V,
∂x2

Et
ϕ(t) = C2 e−i ~ Ĥψ = Eψ

Mark Benazet Castells | ETH Zürich 9/31

T.I.S.E.

T.I.S.E.

Ĥψ = Eψ

Solving the Time-Independent Schrödinger Equation (T.I.S.E.) provides us

with ψ(x), which, when combined with the known temporal component
iE
ϕ(t) = e− ~ t , fully determines Ψ(x, t).
iE iE
In these separable solutions, |Ψ|2 = ψ ∗ e ~ t · ψe− ~ t = |ψ|2 , they are
notable for their time-independent probability density, characterizing
them as stationary states.

Mark Benazet Castells | ETH Zürich 10/31

Stationary States

Stationary States
In the context of separable solutions, where Ψ(x, t) = ψ(x) · ϕ(t), we
observe that:

• The expectation value of any observable hQi remains constant over

time, i.e., ∂hQi
∂t = 0.
dhxi
• In particular dt = 0 → hpi = 0

• For the Hamiltonian 2 2

q operator, we find hHi = E and hH i = E ,
leading to σH = hH 2 i − hHi2 = 0. Thus, energy measurements
in a stationary state always return the specific value E, indicating a
precisely defined total energy.

Mark Benazet Castells | ETH Zürich 11/31

General Solutions to the T.D.S.E.

General Solutions to the T.D.S.E.

• All other T.D.S.E. solutions can be expressed via separable solutions
given the linearity of the T.D.S.E.

∞
iEn
cn ψn (x)e−
X
t
Ψgeneral (x, t) = ~

n=1

• This formula represents the general wave function as a sum of

separable solutions, each with its own coefficient cn , spatial part
iEn
ψn (x), and temporal part e− ~ t .
• We get ψn and En by solving Ĥψn = En ψn (Eigenvalue Equation)

Mark Benazet Castells | ETH Zürich 12/31

General Solutions to the T.D.S.E.

• ψn (x) represents the probability amplitude when the particle has

energy En .

• Ψgen (x, t) is not a stationary state; expectation values depend on

time.
P∞
• Coefficients cn determined by the initial state Ψ(x, 0) = n=1 cn ψn (x).

• |cn |2 indicates the probability of measuring the energy En .

• Normalization condition: |cn |2 = 1.

P

Mark Benazet Castells | ETH Zürich 13/31

General Solutions to the T.D.S.E.

A rough sketch of what a linear combination might look like at t = 0.

Ψ(x, t)

ψ1 ψ2 Ψgeneral = √1 (ψ1 + ψ2 )
2

Mark Benazet Castells | ETH Zürich 14/31

Motion of the Particle with Zero Potential

Motion of Particle with Zero Potential

Given the time-independent Schrödinger equation (T.I.S.E.) for a particle
in a region where the potential energy V (x) = 0:

~2 d2 ψ(x)
− = Eψ(x),
2m dx2

we arrive at a form analogous to the harmonic oscillator equation from

classical physics:
d2 ψ(x)
= −k 2 ψ(x),
dx2
q
where k = 2mE
~2
represents the wave number, related to the particle’s
momentum p by k = ~p and to the wavelength λ by k = 2π
λ .

Mark Benazet Castells | ETH Zürich 15/31

Motion of the Particle with Zero Potential

• Standing Wave Solutions: characterized by

ψstanding (x) = A cos(kx) + B sin(kx),

• Traveling Wave Solutions: expressed as

ψtraveling (x) = Ceikx + De−ikx ,

Note: The distinction between standing and traveling wave solutions lies
primarily in their boundary conditions.

Mark Benazet Castells | ETH Zürich 16/31

Free Particle

Free Particle
A free particle is one that moves without experiencing any external forces,
meaning the potential energy, V (x), is zero everywhere.
q
Assuming a solution of the form ψk (x) = Aeikx , where k = ± 2mE ~2
,
leads to the general solution for the wave function in both space and time:

Ψk (x, t) = Aei(kx−ωt) ,

2
with ω = ~k2m representing the angular frequency of the wave. k > 0
defines a wave moving in positive x directions and k < 0 defines a wave
moving in negative x directions

Mark Benazet Castells | ETH Zürich 17/31

Free Particle

• Since there are no boundaries, k can take any value, allowing for
any positive energy E.

• The wave function Ψk (x, t), however, is not normalizable over all
space, as its integral over −∞ to ∞ diverges. This indicates that
such states cannot represent physical particles with a definite energy.

Therefore, Quantum Mechanics states the Free Particle with a definite

energy do not exist!

We can fix this by making a continuous linear combination of solutions

instead of a discrete.

Mark Benazet Castells | ETH Zürich 18/31

Free Particle

Wave Packets and Continuous Spectrum

To address the limitations of plane wave solutions, a more physical rep-
resentation of a free particle is given by a wave packet, Ψgen (x, t), a
continuous superposition of plane waves:

" !#
1 ∞ ~k 2
Z
Ψgen (x, t) = √ g(k) exp i kx − t dk,
2π −∞ 2m
Z ∞
1
where g(k) = √ Ψ(x, 0)e−ikx dx
2π −∞

This approach yields a normalizable wave function that can represent a

localized particle.

Mark Benazet Castells | ETH Zürich 19/31

Free Particle

ψ(x)
2

x
−6 −4 −2 2 4 6

−2

Mark Benazet Castells | ETH Zürich 20/31

Infinite Square Well

Infinite Square Well

• The Infinite Square Well (ISW) is a fundamental quantum mechanics
problem illustrating quantization in a confined potential.

• It models a particle trapped in a one-dimensional box with infinitely

high walls (ψ(0) = ψ(a) = 0).

• Potential V(x):
(
0 for 0 ≤ x ≤ a
V (x) =
∞ otherwise

∂ 2 ψ(x)
• Solve ∂x2
= −k 2 ψ(x) using standing wave ansatz!

Mark Benazet Castells | ETH Zürich 21/31

Infinite Square Well

Wave Function and Energy Levels in ISW

Solutions to TISE in ISW are defined by:

n2 π 2 ~2
r
2 nπx
 
ψn (x) = sin , En = , n ∈ Z+
a a 2ma2

Mark Benazet Castells | ETH Zürich 22/31

Infinite Square Well

Wave Function Characteristics

a
• Alternating even and odd symmetries about x = 2 (if wave centered
in x = a2 ).
• Increase in nodes with quantum number n.
(
0 if m 6= n
• Orthogonality: hψm |ψn i = δmn , ensuring indepen-
1 if m = n
dence of states.
• Completeness allows any function f (x) within the well to be expanded
as a series:
∞ Z a
ψn∗ (x)f (x) dx
X
f (x) = cn ψn (x), cn =
n=1 0

Mark Benazet Castells | ETH Zürich 23/31

Infinite Square Well

ψ2 Given a general normalized function

ψgen ψgen = c1 ψ1 + c2 ψ2 , compute coef-
ficients c1 , c2 via inner (scalar) prod-
uct defined in the L2 space:
Z
c2 cn = ψgen (x)ψn (x)dx,

This illustrates, very roughly and

ideal, how ψgen projects onto the
c1 ψ1 basis functions ψ1 and ψ2 , akin to
vector projection in algebra.

Mark Benazet Castells | ETH Zürich 24/31

Infinite Square Well

Energy Quantization in ISW

~2 n2 π 2
• Energy levels are discrete: En = 2ma2
.

• The ground state (E1 ) represents the lowest energy state, with En>1
denoting excited states.

• Energy levels scale with n2 .

• Confinement leads to higher energy: Reducing the size of the well

increases the minimum energy.

Mark Benazet Castells | ETH Zürich 25/31

Infinite Square Well

E
∞ ∞

E3 ψ3 (x)

E2 ψ2 (x)

E1 ψ1 (x)
x
L

Mark Benazet Castells | ETH Zürich 26/31

Clicker Questions

Clicker Questions

Mark Benazet Castells | ETH Zürich 27/31

Exercises

Exercises

Exercise 1

Hint: Start by expressing σx and σp using the definitions of standard

deviation for position and momentum. For the nth state, evaluate the
integrals for hx2 i, hxi2 , hp2 i, and hpi2 . Recall the uncertainty principle:
σx σp ≥ ~2 .

Mark Benazet Castells | ETH Zürich 28/31

Exercises

Exercise 2

Together

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Exercises

Exercise 3

Together

Mark Benazet Castells | ETH Zürich 30/31

Questions?
THANK YOU!