Problems with the classical planetary model of

the atom
• Does not explain why electrons do not
eventually lose all of their kinetic energy
via EM radiation and should crash into
the nucleus  the atom would collapse!!
• Does not explain discrete nature of the
energy in atoms (IP, EA, etc.)
• Does not explain periodic trends
• Does not explain “magic numbers” – the
structure of the periodic table
The explanations were provided by a new theory:
Quantum Mechanics
 The Fifth Solvay Conference
(October 1927)

A. Piccard, E. Henriot, P. Ehrenfest, E. Herzen, Th. De Donder, E. Schrödinger, J.E. Verschaffelt, W. Pauli, W. Heisenberg, R.H. Fowler,
B. L. Brillouin; P. Debye, M. Knudsen, W.L. Bragg, H.A. Kramers, P.A.M. Dirac, A.H. Compton, L. de Broglie, M. Born, N. Bohr;
I. Langmuir, M. Planck, M. Skłodowska-Curie, H.A. Lorentz, A. Einstein, P. Langevin, Ch. E. Guye, C.T.R. Wilson, O.W. Richardson
Fifth conference participants, 1927. Institut International de Physique Solvay in Leopold Park.
29 participants, 17 Nobel Prize winners (one - twice)
The Heisenberg’s Uncertainty Principle
Werner Heisenberg, 1927
 The Heisenberg’s Uncertainty Principle

 Position and momentum of a

x  p  particle cannot be known
2 precisely at the same time
Position and momentum are conjugated variables

h Werner Heisenberg
  1.054572 1034 J  s - Planck’s constant 1927
2

Linear momentum:
p=mv
Uncertainty in
momentum 
uncertainty in
velocity
 The Heisenberg’s Uncertainty Principle

Electron’s position x and momentum p are like a squeeze ball: if you try to
squeeze it in one dimension (e.g., x), it expands in the other dimension (p)
 Motion in Coulomb Potential
z
electron
Energy - charge -e
nucleus r
r charge +Ze
+
x
0 y
E – total energy
K.E.
V(r) – potential energy
Coulomb Potential:
E=0 (zero energy)
2
is defined as state with Ze 1
V (r )  
r
4 0 r
V (r )  
As electron collapses onto the nucleus (r0), mv 2 ???
K.E.   
2
 Classical Theory of Atom:
Motion in a Coulomb potential
1D: 3D: z
nucleus electron electron
charge +Ze charge -e
1 Ze 2 - charge -e
+ -
x V (r )   nucleus r
0 x
4 0 r charge +Ze
+

V(x) x
x y
E V(r)
 - Total energy E can r
V(x) assume any value E
under classical EOM

The electron will oscillate back  - Oscillatory/orbital

and forth between the classical
turning points motion of e- involves The electron will orbit

1 Ze 2
acceleration and around the nucleus
x1,2   (planetary motion).
4 0 E deceleration of an
electric charge (e-),
there will be radiation
of EM waves.
Problems with Rutherford’s Model of the Atom
• Electrons are charged particles
• Charged particles moving with acceleration give off energy via
EM radiation
• Therefore, the atom should constantly be giving off energy
• The electrons would eventually lose all of their kinetic energy
and should crash into the nucleus  the atom would
collapse!!
Rutherford
(1911)

Heizenberg: ain’t gonna happen!!!

(1927):

x  p 
2
 Particles behave like waves
Wave-Particle Duality Waves behave like particles

Luis de Broglie
 Particles behave like waves
Wave-Particle Duality Waves behave like particles

Luis de Broglie (1924)

Particle with momentum p=mv
should behave like a wave with wavelength

h h
dB   de Broglie wavelength
p mv

h  6.626  1034 J s Planck constant

h
dB 
mv

m v
A seagull floating on the ocean moves up and
down as waves pass.
 Electromagnetic Radiation
• Matter is made up of particles, which have mass and
whose motion is described by classical trajectories
(position, velocity, acceleration, etc.)
• Electromagnetic (EM) Radiation (both visible and
invisible) is one mechanism of how energy can be
transferred between particles
• Electromagnetic radiation travels in waves
• All EM waves are characterized by their
velocity, wavelength, frequency, and amplitude
 Electromagnetic Waves
• velocity = c = speed of light
– 2.997925 x 108 m/s (only in vacuum!)
– all EM waves travel at the same speed (only in vacuum!)
• wavelength =  = distance between two consecutive
peaks or troughs in a wave
– generally measured in m, μm, or nm (1 nm = 10-9 m)
• frequency = = the number of waves that pass a point
in space in one second
– generally measured in Hertz (Hz),
– 1 Hz = 1 wave/sec = 1 s-1
• c= (units: c [m/s]=  [m]  [s-1])
• amplitude = A = measure of the max. magnitude of the
electric/magnetic field of the EM wave - determines
“brightness” or intensity
The wavelength of a wave is the distance
between peaks.


2 ( k -vector points in the
wave vector: k direction of wave’s
 propagation velocity)
The flames of metal salts are often
brightly colored.
 Electromagnetic Waves:
color determined by wavelength.
 Types of Electromagnetic Radiation

• Radiowaves  > 0.01 m, low frequency and energy

• Microwaves 10-4m <  < 10-2m
• Infrared (IR)
– far IR 10-4 <  < 10-5 m
– Mid IR 10-5 <  < 2 x 10-6 m
– near IR 2 x 10-6 <  < 8 x 10-7 m
• Visible 8 x 10-7 <  < 4 x 10-7 m
• Ultraviolet (UV)
– near UV 4 x 10-7 <  < 2 x 10-7 m
– far UV 2 x 10-7 <  < 1 x 10-8 m
• X-rays = 10-8 <  < 10-10 m
• Gamma rays =  < 10-10 m
The different wavelengths of electromagnetic
radiation.
 Wavelength and frequency of light

c
• c= 

• Speed of light c = 2.997925 x 108 m/s

• Example:
green light  = 5 10-7 m
3 108 m/s
c
   6.7  1014 -1
s
 5  10 m
7
 Particles behave like waves
Wave-Particle Duality Waves behave like particles

Luis de Broglie (1924)

Particle with momentum p=mv
should behave like a wave with wavelength
h h
dB   de Broglie wavelength
p mv

Max Planck
 Electromagnetic radiation (a beam of light) can be
pictured in two ways: as a wave and as a stream of individual
packets of energy called photons.

Copyright © Houghton Mifflin Company.All rights reserved. 10–22

 Planck’s Theory of Radiation

• Light can be thought of as either waves OR as a

stream of particles
• Light energy comes in discrete portions called
quanta or photons
• Photons have fixed amounts of energy
(Basis of quantum theory)
• The energy of the photon, E, is directly
proportional to the frequency of light, 
– Higher frequency = More energy in photons

E = h
A photon of red light (relatively long wavelength) carries less energy than
a photon of blue light (relatively short wavelength) does.
 Plank’s Theory

E = h energy of a single photon

• h = Planck’s constant h = 6.626  10-34 J s
Frequency is related to Frequency and wavelength are
• wavelength: c related to energy of the photon:
 hc
 E  h 
• Example: 
green light  = 5 10-7 m
c3 108 m/s
   6.7  1014 -1
s
 5  10 m
7

E = h 6.71014 s-1  6.626  10-34 J s = 4.44  10-19 J

 Wave interference demo

https://www.youtube.com/watch?v=Iuv6hY6zsd0
Wave Interference
 Wave Interference: Double Slit Experiment
(Original idea: Thomas Young, 1801)
 Light interference demo

https://www.youtube.com/watch?v=9D8cPrEAGyc
 Photons behave like particles
Wave-Particle Duality Particles behave like photons

Luis de Broglie (1924)

Particle with momentum p=mv should behave like a wave with
wavelength
h h
dB   de Broglie wavelength
p mv

h  6.626  1034 J s Planck constant

h
dB 
mv

m v
 Photons behave like particles
Wave-Particle Duality Particles behave like photons

h h
dB   de Broglie wavelength
p mv

Experimental confirmation:
Clinton Davidson and Lester Germer
Davisson, Germer (1927-1928)
Diffraction of electrons off metal shows wave-like interference patterns

2d sin   n
 Historical Background of Quantum Theory
Davisson, Germer Experiment (1927-1928):

e-

d – distance between
crystalline planes
Metal (Ni)

Bragg diffraction for electrons: 2 d sin   n

Diffraction of electrons off metal shows wave-like interference patterns

 Historical Background of Quantum Theory
Davisson, Germer Experiment (1927-1928):

Bragg diffraction for electrons: 2 d sin   n

Diffraction of electrons off metal shows wave-like interference patterns
 Photons behave like particles
Wave-Particle Duality Particles behave like photons

h h
dB   de Broglie wavelength
p mv

h  6.626  1034 J s Planck constant

Momentum: p  mv
2
m v 1 2 p
Kinetic Energy: K .E.  mv 
2 2m
 de Broglie wavelength is connected to particle’s
momentum and kinetic energy,
 velocity
 and its mass!!!
 Photons behave like particles
Wave-Particle Duality Particles behave like photons

h h
dB   de Broglie wavelength
p mv

h  6.626  1034 J s Planck constant

 Wave-like behavior becomes important when

de Broglie wavelength is of the same order of
magnitude as the length scale of motion, l

When dB  l , wave-like behavior is not apparent – classical limit

When dB ~ l , wave-like behavior is apparent – quantum limit
De Broglie wavelength and the classical limit
 Wave Interference: Double Slit Experiment
(Original idea: Thomas Young, 1801)
• 1752: Benjamin Franklin discovered that lightening is a flow
of electricity.
• Further studies of electrical charges through gases and in
vacuum
• 1897: J.J. Thompson  Cathode Ray Tube.

1856 - 1940
Double-slit experiment with
electrons
 Double-slit experiment with
electrons

For a single electron going through

the double-slit,
The outcome is uncertain.
The probability follows a
wave interference pattern.
 The Heisenberg’s Uncertainty Principle
Werner Heisenberg, 1927

 
h
 1.054572  1034 J  s
x  p 
2 2
- Planck’s constant
Position and momentum are conjugated variables

Mathematical definition of uncertainty:

(Standard deviation)

2
x   x  x2  x
2
p   p  p2  p
Another pair of conjugated variables:
Energy and time Fifth Solvay Conference (1927)
– also connected by an uncertainty principle Einstein (disenchanted with Heisenberg's
Uncertainty Principle):
 "God does not play dice"
E  t  Bohr:
2 "Einstein, stop telling God what to do"
 Plane Wave
 x 
f ( x )  A cos  2   t    A cos(kx  t )
  
λ - wavelength

2
k - wave vector
1.0 
0.5 A - amplitude  - cyclic frequency
f(x)

0.0
  2 - angular frequency
-0.5 
v ph    - phase velocity
-1.0 k

-10 -5 0 5 10

hk
x
h Two Planck constants:
Momentum (per de Broglie): p    k
 2   h / 2
The plane wave is completely delocalized in space – how can it describe a particle?

Consider a sum (superposition) of several plane waves! - wavepacket

 Wavepacket: a Superposition of Plane Waves
Superposition (sum) of several plane waves:
n Note:
f ( x )   Ai cos(ki x  i t ) (Almost) any function f(x) can be represented as a sum of
i 1 cosine (or sine) waves – a.k.a. Fourier series.

One plane wave n=1 p  k1  1.5 (a.u.)

1.0

0.5
f(x)

0.0

-0.5

-1.0

-30 -20 -10 0 10 20 30

x
 Wavepacket: a Superposition of Plane Waves
Superposition (sum) of several plane waves:

Two plane waves

1.0

0.5
f(x)

p  k1  1.5 (a.u.)

0.0

-0.5
 k2  1.6 (a.u.)
-1.01.0

-30 -20 -10 0 10 20 30

0.5
x
f(x)

0.0

-0.5

-1.0

-30 -20 -10 0 10 20 30

x
Wave Interference
 Wavepacket: a Superposition of Plane Waves
Superposition (sum) of several plane waves:
n Note:
f ( x )   Ai cos(ki x  i t ) (Almost) any function f(x) can be represented as a sum of
i 1 cosine (or sine) waves – a.k.a. Fourier series.

Two plane waves n=2 p  k1  1.5 (a.u.)

Δx Δp
 k2  1.6 (a.u.)
1.0

0.5
f(x)

0.0

-0.5

-1.0

-30 -20 -10 0 10 20 30

x
 Wavepacket: a Superposition of Plane Waves
Superposition (sum) of several plane waves:
n Note:
f ( x )   Ai cos(ki x  i t ) (Almost) any function f(x) can be represented as a sum of
i 1 cosine (or sine) waves – a.k.a. Fourier series.

Three plane waves n=3 p  k1  1.5 (a.u.)

Δx
 k2  1.6 (a.u.) Δp
1.0  k3  1.7 (a.u.)
0.5
f(x)

0.0

-0.5

-1.0

-30 -20 -10 0 10 20 30

x
 Wavepacket: a Superposition of Plane Waves
Superposition (sum) of several plane waves:
n Note:
f ( x )   Ai cos(ki x  i t ) (Almost) any function f(x) can be represented as a sum of
i 1 cosine (or sine) waves – a.k.a. Fourier series.

Four plane waves n=4 p  k1  1.5 (a.u.)

Δx
 k2  1.6 (a.u.)
1.0 Δp
 k3  1.7 (a.u.)
0.5
 k4  1.8 (a.u.)
f(x)

0.0

-0.5

-1.0

-30 -20 -10 0 10 20 30

x
 Wavepacket: a Superposition of Plane Waves
Superposition (sum) of several plane waves:
n Note:
f ( x )   Ai cos(ki x  i t ) (Almost) any function f(x) can be represented as a sum of
i 1 cosine (or sine) waves – a.k.a. Fourier series.

Five plane waves n=5

Δx p  k1  1.4 (a.u.)
 k2  1.5 (a.u.)
1.0
 k3  1.6 (a.u.) Δp

0.5  k4  1.7 (a.u.)

 k5  1.8 (a.u.)
f(x)

0.0

-0.5

-1.0

-30 -20 -10 0 10 20 30

x
 Wavepacket: a Superposition of Plane Waves
Superposition (sum) of several plane waves:
n Note:
f ( x )   Ai cos(ki x  i t ) (Almost) any function f(x) can be represented as a sum of
i 1 cosine (or sine) waves – a.k.a. Fourier series.

Ten plane waves n=10 p  k1  1.3 (a.u.)

Δx
 k2  1.4 (a.u.)
1.0  k3  1.5 (a.u.)

0.5
 k4  1.6 (a.u.)
 k5  1.7 (a.u.)
f(x)

0.0 Δp
 k6  1.8 (a.u.)
 k7  1.9 (a.u.)
-0.5

-1.0  k8  2.0 (a.u.)

-30 -20 -10 0 10 20 30  k9  2.1 (a.u.)
x
 k10  2.2 (a.u.)
 Wavepacket is a Superposition of Plane Waves
As we add more and more waves:
The wavepacket becomes more localized in space, but the momentum
(i.e., wavevector and/or wavelength) becomes less well defined.

Δx~50
1.0
Δp~0.1
n=2 0.5
f(x)

0.0

-0.5

-1.0

-30 -20 -10 0 10 20 30

x p
Δx~5

1.0
Δp~1
n=10 0.5
f(x )

0.0

-0.5

-1.0

-30 -20 -10 0 10 20 30

x p
 The Heisenberg’s Uncertainty Principle

Electron’s position x and momentum p are like a squeeze ball: if you try to
squeeze it in one dimension (e.g., x), it expands in the other dimension (p)