de Broglie Relationship

between  and p
Einstein'ss Relationship: E = mc2
Einstein
Planck's Relationship: E = h
Th
Therefore,
f mc2 = h
h = hc/
h /
mc = p = h/
 h/p
= h/ for
f a photon
h t
If we assume that p is the momentum
of a particle as well as a photon,
photon then

h h
D   deBroglie
p mv
 ConcepTest #1
Order the de Broglie wavelengths of the following objects:
1. An electron (m = 9 x 10–31 kg) 3.7 x 10-10 m
with velocity 2 x 106 m/s
2 A baseball (m = 0.15
2. 0 15 kg) 4 x 10-35
35 m
with velocity 100 mph ( 45 m/s)
3. A neutron (m  1.9 x 10-27 kg) 1.7 x 10-10 m
with
i h velocity
l i 2000 m/s /

A. 1 > 3 > 2
B
B. 2 > 1 > 3
C. 3 > 2 > 1
D. 2 > 3 > 1
E. 3 > 1 > 2
 Particle in a Box
l
L

v
M

The particle of mass M is confined to move in one dimension over a distance L.

I iis shown
It h moving
i with
i h a velocity
l i v to theh right.
i h
If we impose a standing wave condition for the matter waves associated with M,
then the standing wave condition for the box becomes

n
L= with n = 1, 2,3,...
2
 Particle in a Box
Substituting the deBroglie condition gives n h
L= with n = 1, 2,3, 
2 p
rewriting,
nh
p=
2L

Using the relation that E = p2/2M, we obtain

2 2 2
p nh
En   2
with
ith n = 1,
1 2,
2 3,
3 ...
2 M 8ML
Quantized Energies!!!
The exact result!
Thus we obtain the following energy level picture:
 Particle in a Box

NOTE!!
More later

Now, e.g. h2 2 2

E3  E2  5 5
8ML 2
2ML2
 Standing Waves
Defined by Boundary
Conditions and
Numbers of Nodes
We have no idea what the
standing
g waves represent.
p
We will discover that the
square of the wave
amplitude
lit d iis a probability
b bilit
distribution for the
location of the particle.
p
  n x 
Thus  As sin   dx  1
2 2
0
  
2
or As  for any n

 Example
p - butadiene

H H E3 - E2, the lowest abs energy

H C C
C C H
H H
The four  electrons are relatively free to move along the carbon chainchain,
and are primarily located above and below the plane of the molecule.
The  bonds are in-plane and make up the molecular framework. If we
know the length
g of the molecule (we ( do: call it L),
), we can treat the four 
electrons as though they were constrained in a box of length L. The  and
 electrons are also spatially separate, so have minimal interactions.
Calculate the energy levels of an electron (mass me) in a box of length L.
Add in the Pauli Principle, allowing no more than two electrons per level.
Then the following picture emerges.
The first optical absorption corresponds to E3 - E2. Correct within 15%
 Bohr Model of Atom
Circular electron orbit around nucleus
Angular momentum, L, of electron is quantized:
 
Quantized because L  mv  r  mvr
and 2πr = n = nh/p = nh/mv n = 1,2,3, . . .
de Broglie Wavelength for Electron must
Form a Standing Wave

P+ P+
 Bohr Model of Atom
Circular electron orbit around nucleus
Angular momentum, L, of electron is quantized:
 
Quantized because L  mv  r  mvr
and 2πr = n = nh/p = nh/mv n = 1,2,3, . . .
h
L  mvr  n  n
2
In order for a a circular orbit to be stable
Centripetal force = Coulombic force
mv 2 Ze 2

r 4 0r 2
Assume that the electron does not emit radiation while in a stable orbit
2
n
r a0 (where a0  Bohr radius  52.92 pm)
Z
Bohr Model of one electron Atom
-e
Z 2e 2
En   with
h n = 1,
1 22, 3
3, 
8 0n a0
2

+Ze

Electronic transitions occur between two states with energies E1

and E2 and yields a spectral frequency:
h = E2 – E1

Bohr model is exact for one electron atoms, but it fails

badly for He or anything else. There was no clear way to
systematically improve the calculation.
There is no real idea “what
what the electron is doing.
doing ”
More is needed: real quantum mechanics
 Ionization Energy of H Atom

What is the ionization energy of the H atom?

Use the Rydberg equation with n1= 1, n2= ∞..

1  1 1 
   R 2  2 
 n n 
 1 2 

IE(H) = 2.18 x 10–18 J = 13.6 eV

 Light Emission from the
H d
Hydrogen n At
Atom
m

x
Line Spectrum of Hydrogen Atom
 Transitions
“Paschen”
for the
Hydrogen Atom
“Balmer”

1  1 1 
   R 2  2 
 n n 
 1 2 

R = Rydberg constant
= 1.0968 x 107 m-1
“Lyman”
 Sample Problem (11
(11.39)
39)
(a)Calculate, on the basis of the Bohr theory, the linear
velocity of an electron (mass = 9.11 x 10–31 kg) in the
ground state of the hydrogen atom. (Ans: 2.19 x 106
m/s)
(b) To what de Broglie wavelength does this velocity
correspond? (Ans: 3.32
3 32 x 10–10 m)
(c)) Deduce an equation for the de Broglie wavelength,
n a Bohr orbit
in or t of quantum num
numberr n, w
with
th Z=1,
Z , inn
terms of a0 and n. (Ans: =2na0)
(d)What is the ratio of the circumference of a Bohr
orbit of quantum number n to the de Broglie wavelength?
(Ans: 2n2a0/2na0 = n)
Wave-Particle Duality
y Leads to
Uncertainty Principle
Cannott k
C know position
iti & momentum
t or
energy & lifetime precisely

Position (q) & Momentum (p) Uncertainty

 
q p  or q u 
2 2m
Energy (E) & Lifetime (t) Uncertainty


E t 
2
 Bohr Microscope
Uncertainty Principle
•Must detect at least one photon
• Resolving power of microscope:

x 
sin 
Ph t momentum
•Photon t = h/
• observed photon may have been
y
scattered anywhere in  
•Conserving momentum means that
the particle got momentum from
the encounter
encounter. Amount unknown by
2p sin  because only know - <  < .
• So 2h sin 
 px 
x 
 2h sin 
•Means x p x
  2h  
sin  
Uncertainty in Electron Position
An electron moving g near an atomic nucleus has
a speed of 2 x 106 ± 1% m/s. What is the
uncertainty in its position?

Answer: ≥ 3 x 10–10 m = 300 Å

This speed is approximately that of a 1s
electron
l t iin H,
H and
d D is
i 300 x greater
t ththan the
th
diameter of the atom (10–10 m), so we have no
precise idea where in the atom the electron is
p
located!

This result has profound implications for the atomic

model - we cannot assign fixed paths for electrons.
 Postulates for Quantum Mechanics
Consider a system
y with N degrees
g of freedom.
1. There exists a function (q1 . . . qN ,t) that contains all
information available for this system. It is called the
state function or wave function
function. Here q represents
coordinate(s). Properties of :
a. * is a probability density Born hypothesis

b.   * dq  1 (normalized)

 2 
c. , , and must be continuous.
qi q 2
i
d (q1 . . . qN,t)
d. t) must be a single valued function of its
arguments