CHEM 1480 Spring 2021

Quantum Mechanics: General Principles

The Postulates of Quantum Mechanics

• Postulate #1: Every physical system is characterized by one or more
stationary states, each specified by a normalized wavefunction that
satisfied the time independent Schrödinger equation (TISE).
• The wavefunction contains all information about the properties of
the system. It must be
• _______________________________

• _______________________________

• _______________________________

• _______________________________ (in most cases)

• Born’s interpretation: What does the wavefunction physically

represent?
• The probability of finding a particle described by in a given
region is given by

(1)

• The particle must be found somewhere within the system

boundaries. This requires all wavefunctions to be
_________________ so that the probability of finding the particle
within the system boundaries is unity

(2)

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• If a set of are solutions to the TISE for a given system, they must
be orthonormal (orthogonal and normalized), which means that

(3)

• Postulate #2: for every observable physical quantity ⌦ in classical

mechanics, there exists a corresponding operator ⌦ ˆ in quantum
mechanics.
• An operator provides the __________________________________
to be applied to a function.
d
✏D̂ =
• For example, if we have an operator dx, and a function

✏g(x) = x2, then

(4)

• Postulate #3: Each measurement of an observable quantity must yield

an eigenvalue ! of ⌦ˆ that satisfies

(5)

• In this eigenvalue equation, ! is a constant and is an eigenfunction

ˆ.
of ⌦
• We also want real eigenvalues. This means that all imaginary
components must cancel when the eigenvalue equation is evaluated.

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• Operators that yield real eigenvalues are called Hermitian

operators.
• All operators we use in quantum mechanics will be Hermitian

Physical Observables and Operators

Observable 1D Operator 3D Operator

Position x̂ = x r̂ = xi + yj + zk
✓ ◆
d i@ j@ k@
Momentum p̂ = i~ p̂ = i~ + + = i~r
dx @x @y @z

Potential Energy V̂ = V (x) V̂ = V (x, y, z)

✓ ◆
~2 d 2 ~2 @2 @2 @2 ~2 2
Kinetic Energy T̂ = T̂ =
2m @x 2
+ 2+ 2
@y @z
=
2m
r
2m dx2

Total Energy ~2 d 2 ~2 2
Ĥ = + V (x) Ĥ = r + V (x, y, z)
(Hamiltonian) 2m dx2 2m
✓ ◆
@ @
Lˆx = i~ y z
@z @y
✓ ◆
@ @
Angular Lˆy = i~ z x
@x @z
- ✓ ◆
Momentum @ @
ˆ
Lz = i~ x y
@y @x
L̂ = Lˆx i + Lˆy j + Lˆz k

★ Example: Is the function eimx an eigenfunction of the momentum

operator? If so, what is the eigenvalue?

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• Operators and the Heisenberg Uncertainty Principle

• There is a limit on how well we can measure two observables that

can be measured simultaneously

• For example, when measuring position (x) and momentum (px),

their uncertainties have a _________________________

(6)

• Note that since px = mvx

(7)

• This implies that only ________________________ (like

electrons) must have relatively large uncertainties in x and vx

• Observables that are related through the uncertainty principle

have operators that _______________________. This means
that:

(8)

• Postulate #4: The average of a series of unbiased measurements of the

ˆ is given by the expectation value
quantity represented by ⌦

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(9)

• Many times the average value and expectation values will be the
____________________.

• However, if is not an eigenfunction of an operator, we can still (at

least) obtain an average value.

• Postulate #5: The state of a system evolves in time according to the time
dependent Schrödinger equation (TDSE)

(10)

✏
• The total wavefunction is given by the following product

(11)

• Since we can ________________________ the time component

from the stationary states described by , we can simply use the

TISE, as long as the system does not evolve with time.

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CHEM 1480 Spring 2021

A simple quantum problem: Particle in a Box (PiB)

• Imagine a particle with mass m
confined to a 1D “box” of length
a.

• The confinement occurs since

the potential energy at the “walls”
of the box is infinite, but zero
inside the box. These are the
_______________________ of
our system.

(12)

• The TISE for inside the box is

(13)

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• The general solution to this ODE is

(14)

• Now we can apply our boundary conditions

• Since
✏ (x) must equal zero at x = 0, we must set _____________

since ____________________.

✏ (x) must equal zero at x = a. We know that the sine function

• Also,

goes to zero when _________________________________. So, we

require that _____________________.

• This leaves us with

(15)

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• A is the amplitude of our wavefunction. We can find the value of A by

applying our normalization condition (equation 2). We can integrate✏ 2
✏ (x) is real valued. We will need the following standard integral.
since
Z
x sin 2bx
sin2 bxdx = (16)
2 4b

✏ (x) for the 1D PiB have the form

• The set of

(17)

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• Now we need the energy eigenvalues, which we can get by substituting

n (x) back into the TISE.

(18)

✏En 6= 0 when n = 1. This is called the

• Note that

________________________________, which can never be removed

from the system, a consequence of the Uncertainty Principle.

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★ Example: What is the average

position hxi for 1 (x) ?

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• The probability densities for the

1D PiB can be plotting✏ 2.
2
• Note that as n increases,
✏

approaches a
________________________.

• This is an illustration of the

________________________,
which states that at sufficiently
high energies, quantum
mechanics agrees with
classical mechanics.

PiB in 3D
• We can very easily extend our 1D PiB
problem into 3D. If we consider a 3D
box with dimensions a × b × c, where V
= 0 inside the box and V = ∞ elsewhere.
• The TISE can be written as

(19)

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• We can assume that \psi (x, y, z) can be written as a

__________________ of 1D PiB wavefunctions that depend on each
variable. This gives

(20)

• The total energy is ______________.

(21)

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• In the 3D PiB, it is possible to have ____________________________

or states with the same energy. This is especially true when
______________ is introduced.
2 2 2
• If✏(nx + ny + nz ) is ________________________ for any two or more

sets of n values, the states will be degenerate.

Real-life Applications of the Particle in a Box Model

• Quantum dots
• Semiconducting nanoparticles with diameters between
_________________.

• At this size, energies become ________________________ “again”.

• The band gap for quantum dots depends on the ________________,

which can be explained using the PiB model.

• Quantum dots fluoresce at very __________________ wavelength

ranges that depend on their ___________________, making them
useful in many applications.

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• Tunneling

• In the PiB model, we observe that when the ___________________,

the wavefunction can be found in ____________________________
regions.

• As a result, the wavefunction can “tunnel” through certain potential

energy barriers and make it to other “side.

• Scanning tunneling microscopy (STM) is an application of this

phenomenon.

• In STM, electrons tunnel from the probing tip to the sample,

producing a _________________.

• This current varies exponentially with the _________________

between the tip and the sample, allowing for surface imaging on
the ___________________________ level.

• STM can only be used to image electrically

_________________________________________ materials.

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