Lecture 17: Intro.

to
Quantum Mechanics
• Reading: Zumdahl 12.5, 12.6

• Outline
– Basic concepts.
– A model system: particle in a
box.
– Other confining potentials.
 Quantum Concepts
• The Bohr model was capable of describing the
discrete or “quantized” emission spectrum of H.

• But the failure of the model for

multielectron systems combined
with other issues (the
ultraviolet catastrophe,
workfunctions of metals, etc.)
suggested that a new description
of atomic matter was needed.
 Quantum Concepts
• This new description was known as
wave mechanics or quantum mechanics.

• Recall that photons and

electrons readily demonstrate
wave-particle duality.
• The idea behind wave mechanics
was that the existence of the
electron in a fixed energy
level could be visualized as a
“standing wave”.
Quantum Concepts
Q: What is a standing wave?

A standing wave is a
motion in
which translation of
the wave does
In
notthe guitar string
occur.
analogy
(illustrated), note
that standing
waves involve nodes in
Notenoalso that integer
which
and motion
half- of the string
integer values of the
occurs.
wavelength
correspond to
• Louis de Broglie suggests that for the e-
orbits envisioned by Bohr, only those
orbits are allowed which satisfy the
standing wave condition.

not
allowed
 • Erwin Schrodinger develops a
mathematical formalism that
incorporates the wave nature of matter:

ˆ
H  E

Kinetic Energy
ˆ pˆ2
The Hamiltonian:H   (PE)
x 2m
 
The Wavefunction:

 
E = energy
Q: What is a
wavefunction?
= a probability amplitude

y  Ae   
• Consider a wave: i 2  t 

Intensity =y  Ae Ae  A

2 i2  t   i2  t   2


• Probability of finding a
particle in space: *
 Probability = 
• With the wavefunction, we can
describe spatial distributions
 • Another limitation of the Bohr model was that
it assumed we could simultaneously know both
the position and momentum of an electron
exactly.

• Werner Heisenberg’s development

of quantum mechanics leads him
to the observation that there
is a fundamental limit to how
well one can know both the
position and momentum of a
particle (Heisenbergh
xPrinciple)
Uncertainty  p 
4
Uncertainty in positionUncertainty in momentum
• Example of Heisenberg
Uncertainty:

What is the uncertainty in

velocity for an electron in a 1Å
radius orbital in which the
positional
x = (1 uncertainty
Å)(0.01) = is1 1% of
the radius.
x 10-12 m 34
p 
h

6.626x10 J.s
 5.27x10 23
kg.m / s
4 x 4  1x10 m
12

p 5.27x1023 kg.m /s 7m
v    5.7x10 s Huge!
m 9.11x1031 kg

(Recall the speed of light is

c = 3 x108 m/s)
 Another Example (you’re a quantum wave as
well!):

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%.

p = m v = (80kg)(0.013 m/s) = 1.04 kg.m/s

x 
h

6.626x1034
J.s
 5.07x1035 m
4 p 4  1.04kg.m /s

Very small uncertainty……so, we know

 where you are!
 Potentials and
Quantization
• Consider a particle free to move in 1 dimension:

p
Case: ‘Free’
x
Particle
Potential E = 0
The Schrodinger Equation becomes:
 pˆ 2  pˆ 2
p 2
1 2
ˆ
H    PE  ( p)   ( p)   ( p)  mv  ( p)  E ( p)
2m  2m 2m 2
0
• Energy ranges from 0 to
infinity….not quantized, particle
 Q: What if the position of the particle
is constrained by a potential?

Case: “Particle
inf. in a Box”
Potential E
E = 0 for 0 ≤ x
≤ L
0 E =  for all
0 L
x other x

The possible position of particle is

limited to the dimensions of the box,
0 to L
QM Solution for the particle in
a box
What do the wavefunctions look like?

2 nx 
 x   sin 
L  L 
+ +
+
n = 1, 2, ….
- 

Like a
+ + standing
wave
 
What does the energy look like?

2 2
n h
E
8mL2

n = 1, 2, …


Energy is
quantized

E  
A real-world example:
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
N

What wavelength of light corresponds to E

from n=12 to n=2? 2
h h
2  final initial  2   19
E  n 2
 n 2
 2 2
1  2.8x10 J
8mL 8m(8Å)

  700nm (Observed value 680 nm,

If the length L
of the “box” in the particle in a
box potential is reduced, what do
you expect Vto happen to the
V
energy
levels?

3
4

E E
3 2
2
1 1
• One effect of a “constraining potential”
is that the energy of the system becomes
quantized.

• Back to the hydrogen atom:

0 r
e-

e 2
r V (r) 
P+ r


So, for the hydrogen atom, energy
becomes quantized due to the
presence of a constraining
potential.

Z 2 
0 r E  2.178 x10 18
J 2 
n 
0

Solve
 the
Wave
Equation
e 2
V (r) 
r

Exact q.m. solution is the

Bohr formula!

What is the expected distribution
of energy levels for the harmonic
oscillator?
V V V

E E E

Hydrogen Atom Harmonic Oscillator Particle in a Box