Lecture 18: Quantum Mechanics

• Reading: Zumdahl 12.5, 12.6

• Outline
– Basic concepts of quantum mechanics and
molecular structure
– A model system: particle in a box.
• Demos how Q.M. actually obtains a wave function.
– Confining potentials: Box and Coulomb’s law
• Problems (Chapter 12 Zumdahl 5th Ed.)
– 36, 38, 39, 40, 41, 44(find n also), 45(What
should happen when system does work?), 46
(find visually).
1
 Quantum Concepts

• The Bohr model was capable of describing the

discrete or “quantized” emission spectrum of H.

• But the failure of the model for multi-electron

systems combined with other issues (the
ultraviolet catastrophe, work functions of metals,
etc.) suggested that a new description of atomic
matter was needed.

2
 Wave-Particle Duality
• This new description is known as wave mechanics or
quantum mechanics.
• Recall, photons and electrons readily demonstrate wave-
particle duality.
• The idea behind wave mechanics is that the existence of
the electron in fixed energy levels should be thought of as
a “standing wave”, rather than a particle’s trajectory.
• Think about two ways to describe your travels during the
day, one uses position and time (the classical way), and
the other is just position and probability (the statistical
description).
• Q.M. Provides a way to describe an electron
probabilistically without saying in detail how it moves
from place to place (that idea must be discarded).
3
 Q.M. Concepts: The Standing Wave
Ψ ( x ) = A ⋅ sin ( k ⋅ x )
2π n ⋅π
k≡ = n = 1, 2,3
λ L
n =1 ↑ • A standing wave is a motion in
A
↓ which translation of the wave does
not occur. (A is the amplitude.)
• In the guitar string analogy
n=2
(illustrated), note that standing
waves involve nodes in which no
motion of the string occurs.
• Note also that integer and half-
n=3
integer values of the wavelength
correspond to standing waves; n
must be an integer. 4
 Q.M. Concept: The deBroglie Relation
• Louis de Broglie suggests that for the e- orbits envisioned
by Bohr, only certain orbits are allowed since they satisfy
the standing wave condition.
• Light has momentum (but no mass) and so for light:
hc
Elight = cp = hν =
λ
h
plight =
λ
If true for light, then
true for matter
(particles) as well. not allowed
h
m⋅v = p =
λ
5
Amplitude in a line Amplitude in a circle.
 Amplitude of a periodic function
?
Ψ (φ ) = cos ( m ⋅ φ ) = cos ( m ⋅ (φ + 2π ) )
• Show periodic function circling around 6 times.
• Only integer values of m keep the function in phase when
circling an indefinite number of times.
• This is deBroglie’s idea: If an electron behaved as a
standing wave in the phi (φ) direction then only integer
values of m could keep the wave in phase indefinitely for
any value of φ, not just zero to 2π.

m = 3.1
6
m = 3.0
 Q.M. Concept: Wavefunction
What is a wavefunction? Ψ ( r ) is a ‘probability amplitude’
For Example a wave in one dimension (the guitar string):
Ψ ( x ) = A ⋅ sin ( kx )
Prob = P ( x ) = Ψ ( x ) Ψ ( x ) = A2 ⋅ sin 2 ( kx )
*

• Probability (density) of finding a particle in space is the

absolute square of the amplitude.
• A proper probability must sum to 1, when one explores over
all x. This is a way of saying the particle must be somewhere.
Here the standing wave of the string is confined from 0 to L.
Therefore N L
1 = ∑ P ( xi ) Δx ⇔ 1 = ∫ P ( x )dx
i =1 x =0

• Probability is a statistical description of where the particle is.

Compare to a probability distribution of a student on campus. 7
 Particle (electron) in a box or trap
This is a “salad bowl” model for electron confinement: See the
“corral gallery” at IBM/Almaden
Particle’s position is constrained by any confining potential:
The choices of physical solutions are countable (but
infinite), so ‘quantized’.
inf.
“Particle in a Box” like the
ideal gas molecules; now it is
a quantum particle. Inside the
box the particle just bounces
0
0 L around (no potential energy
x inside) but the particle cannot
The possible positions of particle are get out of the box.
limited to the dimension of the box.
Classically the probability is uniform. 8
 Particle (in a Box) Wavefunction
What do the wavefunctions look like?

0 n=3
• Z12.46
Estimate Prob
Ψ ( x) Ψ ( x ) Ψ ( x)
*
0≤ x≤ L

Probability
6
Amplitude

0 n=2

0 n =1

nπ 2
Ψ n ( x ) = A ⋅ sin ( k ⋅ x ) k= n = 1, 2,3 A=
L L
9
A standing wave: n is an integer counter; keeps track of the different functions.
 Q.M. Concept: A Wave Equation
• Erwin Schrodinger developed a mathematical formalism that
describes matter using waves.
• Why waves: Newton’s and Maxwell’s formulations did not
work. Follow deBroglie. Must try something else.
The Wave Equation: Ĥ Ψ = E Ψ
This is an equation of ‘motion’, but it does not contain time.
It is a statement only about position of a particle in space (in a
probabilistic sense) and the energy of the particle (E). The
wave function (Ψ) describes the particle position.
H is the Hamiltonian, which is the total energy written in terms
of momentum and position. Just like the Bohr Model:
H = T +V
T = 12 mv 2 = 21m p 2 V = V (r ) 10
 Potentials and Quantization
• Any confining or binding potential will lead to quantized
states (distinct energies and wave functions)
• Aids in understanding how the wave functions are
determined.
Hamiltonian Ĥ = T + V
Kinetic Energy (T): (True for every problem) T = 2m
1 p2

Potential Energy (V): (three examples)

Free Particle V ( r ) = 0 (not confined)
⎧⎪V ( x ) = 0 0 ≤ x ≤ L
Particle in Box ⎨
⎪⎩V ( x ) = ∞ otherwise
e2 Z
Hydrogen Atom V (r) = − Coulomb's Law
4πε o r 11
 Implementing Schrödinger’s Equation
• Schrodinger’s recipe (called the “correspondence
principle”) is to substitute for the momentum of the
particle the derivative process (operator):
Schrodinger Recipe
d 2Ψ
p2Ψ ⇒ pˆ 2 Ψ = − 2

dx 2
• This turns the energy equation into a second order
differential equation, which can be solved (by look
up/inspection), to give both the wavefunction and the
energy.
• Show how this works: Take two derivatives of the
wavefunction (for the guitar string):
Ψ = A sin ( kx )
d Ψ
2
d 2
sin ( kx )
2
= A 2
= − k 2
A sin ( kx ) = − k 2
Ψ
dx dx
pˆ 2 Ψ = ( k ) Ψ
2
12
 Demonstrate The wave function satisfies the
Schrodinger Equation and Gives the Energies
• Use the guitar string wave function and demonstrate that it
is a (the) solution to the Schrodinger Equation:
• Find the energy of each wave function (for different values
of k). d 2Ψ
If: Ψ = A sin ( kx ) and 2
= − k 2
Ψ
dx
1 2
Hˆ Ψ = E Ψ V =0 Hˆ = Tˆ = pˆ
2m
2 d Ψ d 2Ψ
2
− 2m 2
= E Ψ and − 2
= k 2
Ψ
dx dx
2m Ψ = E Ψ
2 2
k

( k)
2
p2 h
=E= ⇒p= k= (Just what deBroglie said)
2m 2m λ 13
 Summarize: The Schrödinger Equation
• Assume the wave function is the same as the amplitude
wave for a string, and k is some constant, to be determined.

2m ( k ) Ψ = E Ψ
• Using the result that Hˆ Ψ = 1 2

• Now we connect the constant k to the energy E (which is

2m ( k) = E
just a number): 1 2

• If the problem is like a string tethered at the two ends (x=0

and x=L) then we use the amplitude wave for that case,
2π π n
which gives: k = = n = 1, 2,3
λ L
• Because n is an integer, we have an infinite number of
different possible results and a different energy for each
( π )
result, but the energies are quantized. 2

E = En = 2
n 2
14
2mL
 Q.M. Concept: Energy is quantized

( k)
2

E=
2m
⎛ h2 ⎞ 2
En = ⎜ 2 ⎟
n Ψn ( x)
⎝ 8mL ⎠
n = 1, 2,3 ∞ Energy

Amplitude
Show some wave functions
with the energy
associated with each
wave function.
The classical limit (Z12.45)
15
 QM Concept: Uncertainty
• Another error of the Bohr model was that it
assumed we could know both the position and
momentum of an electron exactly.
• Werner Heisenberg’s development of quantum
mechanics leads to the understanding that there
is a fundamental limit to how well one can
know both the position and momentum of a
particle at the same time. There are tradeoffs.
h
ΔxiΔp ≥ 1 = 1
2 2 2π
Uncertainty in position Uncertainty in momentum,
which is mass times velocity
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 Uncertainty (on the small scale) Z12.41a
• Example: What is the uncertainty in velocity for an
electron in a 1Å radius orbit (orbital) in which the
positional uncertainty is 1% of the radius.

Δx = (1 Å)(0.01) = 1 x 10-12 m

Δp =
h
=
(6.626x10−34

=
J.s)
5.27x10−23
kg.m /s
4 πΔx 4 π (1x10 m)
−12

Δp 5.27 x10−23 kg .m / s Huge

Δv = = = 5 .7 x10 7 m

m 9.11x10−31 kg s Near C

So we really have to give up the idea we know (even

roughly) the position and velocity at the same time.
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 Uncertainty (on the large scale) Z12.41b
• Example (quantum description of large objects):
What is the uncertainty in position for a 80 kg student
walking across campus at 1.3 m/s with an uncertainty
in velocity of 1%.
Δp = m Δv = (80kg)(0.013 m/s) = 1.04 kg.m/s

Δx =
h
=
(6.626x10−34
J.s)
= 5.07x10−35 m
4 πΔp 4π (1.04kg.m /s)

Very small……you know where you are.

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 Optical Spectra Z12.44-45
using Particle in Box Energy Levels
• Consider the following dye molecule, the length of which
can be considered the length of the “box” an electron is
limited to:
+
N
L = 8 Å=0.8 nm
hν
N

What wavelength of light corresponds to ΔE from n=1 to

n=2? (A photon/Energy is absorbed by the molecule)
h2 2
ΔE =
8mL 2 ( n 2
final − n 2
initial ) =
h
8m(8 Å ) 2 ( 2 2
− 1) = 2.8 ⋅ 10 −19
J

hc λ ≈ 700nm
E photon =
λ (should be 680 nm, orange)
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Potentials and Quantization (cont.)
• One effect of a “constraining potential” is that the
energy of the system becomes quantized.

• Back to the hydrogen-like atom:

e- 0 r

r −e2
P+ Z V (r) = Z
r

constraining potential
20
 H Atom Potential
• Also in the case of the hydrogen atom, energy
becomes quantized due to the presence of a
confining/constraining potential.

0 r 0

−e′2 Z Schrödinger
V (r ) = Equation
r
Above zero (positive energy
states) the energy is not Recovers the “Bohr” behavior
21
quantized; any K.E. is O.K.