INTRODUCTION TO

QUANTUM MECHANICS
Instructor: Dr. Mehr Nigar
 Failure of the Classical description of Atom
 Light as a wave; characteristics of waves
 Light as a particle; photoelectric effect
 Matter as wave!; Louis de Broglie
 Wave-particle duality; Beginnings of Quantum
Mechanics
Failure of Classical Mechanics

What is wrong in this mathematical

calculation???

Coulomb’s Force Law?

Newtonian Mechanics? F = ma

The laws of classical mechanics no longer work at this size scale!

The Quantum Revolution!

“Will we ever understand the atom?”

(question posed to Niels Bohr)
Bohr: “Yes, we will, but only if we change
what we mean by the word understand.”
“Things on small scale behave like nothing
that you have any direct experience
about.” Richard Feynman (1963)
Assumptions made by Quantum
Mechanics
Light consists of discrete packets of
energy called photons.
Matter and radiation display both wave-like
and particle-like properties.
Properties of Waves

Waves tend to have a periodic variation of

some quantity
Interaction of Waves

Water Waves
Sound Waves
 Amplitude, Wavelength and
Frequency:

Amplitude is defined as the deviation from the average level, it can be positive or
negative.

Wavelength is the distance between the successive maxima or minima.

Frequency is the number of cycles per unit time.
What is the amplitude of the water wave below?

10 m x

12 m

1. 10 m
2. 12 m
3. 5m
4. 6m
Light Waves

Image courtesy of MIT open coursware

Light (electromagnetic radiation) is a periodic variation of an electric field.

Mathematical Description of a Wave I
 If time t = 0 or constant; the electric field of light can be visualized as
function of position, x.

E(x) = a (amplitude), will be maximum when x = …..-, 0, , 2 …..

Intensity = a2
Mathematical Description of a Wave II
 If position x = 0 or constant; the electric field of light can be visualized as
function of time, t. E (0,t) = a Cos (2t)

Units of frequency  = # of cycles / second = Hertz (Hz)

e.g. 5 s-1 or 5 Hz
How fast is a wave of light travelling?

At t = 0

At t = 1/f
(one period)

Speed = distance traveled / time elapsed

Speed =  = f m/sec
1/ f
Speed of EM Radiation

Electromagnetic radiation has a constant

speed, c (the speed of light)

f = c = 2.9979 x 108 ms-1

(c  670,000,000 mph, or 186,000 miles/sec!

Compare light wave A to light wave B as
illustrated below:

light wave A light wave B

1. Light wave A has a
shorter  and a lower
f.
2. Light wave A has a
shorter  and a higher
f.
3. Light wave A has a
longer  and a higher
f.
4. Light wave A has a
longer  and a lower f.
 Electromagnetic Spectrum

Long
Short
Wavelengths
Wavelengths
Low Frequencies
High
Frequencies
Applications of Flourescence

Fluorescent Paint

Quantum Dots

Wavelength of the emitted light is proportional to the size of the quantum dot.
Quantum Dot Displays
Superposition of Waves
Applications of Destructive
Interference
Noise Cancellation Headphones:

Take in the ambient noise waves and inbuilt batteries

Produce waves to cancel out the noise waves
 Lasers
 A laser is source of light that emits the purest, brightest color of any device
known. The word laser is an acronym standing for light amplification by
stimulated emission of radiation. A gas laser is just a discharge tube with
mirrors on each end. One of the mirrors is only partially reflecting, to allow
some light to escape.
 The earliest gas laser (invented in 1961) is the helium-neon laser, which
emits red light of wavelength  = 6.328 x 10-5 cm (632.8 nm); it came into
widespread use in barcode scanning. Calculate the frequency and wave
number of this laser light.
 Solution:
f = c/ = (2.998 x 1010 cm s-1) / (6.328 x 10-5 cm)
= 4.738 x 1014 cycles s-1 = 4.738 x 1014 Hz
wave number = 1/  = 15,800 cm-1
Light as as Particle: The Photoelectric
Effect
Established in 1800’s that light was a
wave.
Diffraction of light was observable
Constructive and destructive interference of
light was observable
Lenard’s Photoelectric Apparatus:
 The Experiment:

By varying the voltage on a negatively charged grid between

the ejecting surface and the collector plate, Lenard was able
to:

Determine that the particles had a negative charge.

Determine the kinetic energy of the ejected particles.

Perplexing Problems:
The intensity of light had no effect on the
kinetic energy of the electrons.

There was a threshold frequency f0 for

electron ejection.

Classical Physics failed to explain these

observations. Lenard won the Nobel Prize
in Physics in 1905!
Graph of number of electrons vs. frequency
Observations:

No electrons were ejected below a certain

threshold frequency, which was different
for each metal.
The number of electrons ejected was not
related to the frequency of the incident
light!
Kinetic Energy of Electrons
Intensity of Light vs. number of
Electrons
Number of electrons as a function of
Intensity:
Einstein’s Observations

y = mx + b
Slope (m) = 6.626 x 10-34 Js

Intercept (b) = (6.626 x 10-34 Js)0

Planck had observed this number much earlier as a fitting constant to explain
Black body radiation.
Einstein’s Relations:
Einstein predicted that a graph of the maximum kinetic energy
versus frequency would be a straight line, given by the linear
relation:
KE = hf - Φ
…Therefore light energy comes in multiples of hv

This was published in his famous 1905 paper:

“On a Heuristic Point of View About the Creation and Conversion of Light”
 Einstein’s Interpretation
A new theory of light:

 Electromagnetic waves carry discrete energy

packets, called photons.

 Energy of a photon is proportional to its frequency.

 More intense light corresponds to a greater number

of photons, not higher energy/photon.

This was published in his famous 1905 paper:

“On a Heuristic Point of View About the Creation and Conversion of Light”
New Model for Photoelectric Effect:

Ei = K.E + 
K.E = Ei - 
If a beam of light with energy = 7.0 eV (1 eV = 1.602 x
10-19 J) strikes a gold surface, what is the maximum
kinetic energy of the ejected electrons.

light (Ei = 7.0 eV)

gold ( = 5.1 eV)

1) K.E. = 12.1 eV
2) K.E. = 5.1 eV
3) K.E. = 1.9 eV
4) K.E. = 7.0 eV
5) No electrons will be ejected.
 Ei = Incident Energy
If f  f0 No electrons are ejected! f0 = threshold frequency
 = Work Function
If f  f0 Electrons are ejected!
 Energy of a photon:
 Energy of a photon must be equal to or greater than the work
function of a metal, for an electron to be ejected.

e- is ejected! e- is NOT ejected! e- is NOT ejected!

In photoelectric effect, light is acting as particles and NOT waves, therefore the energies
cannot add up; like they do in case of waves.
Summary:
 If the incident beam has insufficient energy i.e Ei < , no matter how intense
the beam, electrons will not be ejected.
 If Ei >  then does the intensity of the incident beam has any effect on the
ejected electrons?

Each photon ejects a single electron, therefore the greater the number of incident
photons the higher the number of ejected electrons.
Intensity of light (energy/sec) is proportional to the # of photons emitted/sec.
High intensity means more photons/sec, Unit of Intensity = W = Js-1
NOT more E / photon
Summary of Terminology:
 Photons: also called light, electromagnetic radiation, may be described in
terms of energy,  or f.

 Electrons: also referred to as “photelectrons”, may be described in terms of

K.E., velocity or .

 Electrons DO NOT travel at the speed of light! Speed of an electron ≠ c

Problem 1
 Consider two light sources; a UV lamp ( = 254 nm) and a laser pointer (
= 700 nm), are these two light sources capable of ejecting electrons from
a Zinc plate? ( = 6.9 x 10-19J)
1) What is the energy/photon emitted by the UV lamp?

E = 7.82 x 10-19J, the UV lamp does have enough energy to eject an electron from Zn surface.

2) What is the energy/photon emitted by the Laser pointer?

E = 2.84 x 10-19J, the laser pointer does NOT have enough energy to eject an electron from Zn
surface.

3) What is the total number of photons emitted by the laser pointer in 60 seconds if intensity (I) =
1.00mW

# of photons emitted if the laser pointer is used for 60 s = 2.1 x 1017 photons.
# of photons emitted if the UV lamp is used for 60 s = 7.67 x 1016 photons.

The intensity of light is NOT related to the energy of its photons!

 Problem 2:
 The “electric eyes” used to open doors automatically are based on the
photoelectric effect. The metal surface inside the “eye” which is basically an
evacuated glass envelope containing the surface (cathode) and a
photocurrent collector (anode), continuously provide current until the light
beam that actuates it is interrupted. What is the maximum kinetic energy of
photoelectrons produced by a mercury vapor lamp, emitting 436 nm violet
light, actuating an electric eye of work function 2.1eV?

 K.E = Ei - 
 K.E = hc/ - 

 K.E = 6.626 x 10-34 Js x 2.998 x 108 ms-1 – (2.1 x 1.602 x 10-19Js-1)

436 x 10-9 m

K.E = 1.19 x 10-19 Js-1 = 0.74 eV

Problem 3:
 If a beam of light with energy = 5.0 eV (1 eV = 1.602 x
10-19 J) strikes a gold surface, what is the maximum
kinetic energy of the ejected electrons.
Light Ei = 5.0 eV

gold ( = 5.1 eV)

No electrons will be ejected!

Practical Applications of Photoelectric
Effect:
 Photocell: A vacuum tube with a photosensitive cathode, electrons
flow from cathode to anode to complete the circuit in presence of
light. Can be made responsive to light or to removal of light.

 Photoconductive devices: lead to an increase in the conductivity

of a non-metallic material when exposed to light.

 Solar Cells: act like a battery when exposed to light. Individual solar
cells produce voltages of about 0.6 volts but higher voltages and
large currents can be obtained by appropriately connecting many
solar cells together
Read more:
 <a href="http://science.jrank.org/pages/5169/Photoelectric-Effect-
Applications.html">Photoelectric Effect - Applications</a>
Photon Momentum

If light is a stream of particles, then each

of these particles must have a momentum
(p).
p = hf/c
since c = f
p = h/

‘> 
Beginnings of a New Mechanics!

Louis de Broglie (1892-1987)

p = h/

 = h/p

since p = mv
 = h/mv
Theorized in his PhD thesis (1929) that if light can
behave as a particle and have a momentum, matter
can also have a wavelength related to its momentum!

De Broglie “lifted the corner of a great veil.”- Albert Einstein

Wavelength of Shoaib’s fast ball?

velocity = 100 mph (44.7 m/s)

mass = 162g = 0.162kg
 = h/mv
• 6.626 x 10-34kgm2s-2s / (0.162 kg) (44.7 m/s)

 = 9.2 x 10-35 m

Undetectable!
 Which bowler’s fastball has the longest
wavelength?

100 mph (pak vs New Zealand (27/04/02)

44.7m/s

97.8 mph (Australia vs. S. Africa 08/03/02)

43.7 m/s

http://stats.cricinfo.com/ci/content/records

Ashish Nehra
 = 1.04 x 10-34 m

95.9 mph S Africa vs. India, 03/11/01 87.6 mph India vs. West Indies, 21/04/02
42.9 m/s 39.2 m/s
Wavelength of an electron:

v = 44.7 m/s

e- v = 2.998 x 108 m/s / 1000 = 299,800 m/s

 = h / mv = 6.626 x 10-34 kgm2s-2s / (9 x 10-31kg) (299,800 m/s)

2.46 x 10-9 m = 24.6 Å

 Wave Nature of Electron:
 1925 Davisson and Germer were able to observe electron diffraction
from a Ni crystal.
 G.P Thomson showed that electrons that passed through a very thin
gold foil produced a diffraction pattern.

ELECTRONS have both wave-like and particle like properties.

G.P. Thomson was the son of J.J. Thomson. Both received Noble prizes, J.J. for showing that the electron
is a particle and G.P. for showing that it is a wave!
Matter as wave!

Schrodinger Wave Equation:

Describing electrons by their wave properties.

= Wave Function (a way of representing electron)

E = Binding Energy (of the electron to the nucleus)
H = Hamiltonian operator
Shrodinger Equation:

Wavefunction for electron

Hamiltonian Binding
Operator Energy
Solving the Schrodinger Equation

Finding or wavefunctions or orbitals

Finding E, binding energy of electron to nucleus

Electron as a Particle in a box!
Solving for Hydrogen Atom

m = me = mass of an electron 0 = permittivity constant

e = charge on the electron h = Planck’s constant

me4 = RH = Rydberg’s Constant = 2.18 x 10-18 J

80h2
Now the binding energy En = -RH/n2 n = 1,2,3……..

n = principal quantum number

Quantization of Energies
0 n= Free electron
H+ + e-

-0.061 x 10-18 J
-0.087 x 10-18 J

-0.146 x 10-18 J -RH

42

-0.242 x 10-18 -RH

J 32

-RH
-0.545 x 10-18 J
22

-2.180 x 10-18 J ground state

Significance of Binding Energies
En = -IE of an atom in the nth state

i.e. the amount of energy required to ionize an H atom

The IE for an H atom in the ground state is 2.18 x 10-18 J

first excited state

The IE for an H atom in the first excited state is 5.45 x 10-19 J

What is the IE of a H atom in the 3rd excited state?
0
En
1. -0.09 x 10-18 J
- 0.06 x 10-18 J n=6
2. 0.09 x 10-18 J
- 0.09 x 10-18 J n=5
3. -0.14 x 10-18 J
- 0.14 x 10-18 J n=4
4. 0.14 x 10-18 J
5. -0.24 x 10-18 J - 0.24 x 10-18 J n=3
6. 0.24 x 10-18 J
7. -0.54 x 10-18 J
- 0.54 x 10-18 J n=2
8. 0.54 x 10-18 J

- 2.18 x 10-18 J n=1

Energies of single electron atoms:

 En = - Z2RH Correctly predicts the energy levels for any one electron atom!
n2

He+ 1 electron atom Z=2

Li2+ 1 electron atom Z=3

U(r) = -(Ze)e / 4π0r

Fifth International Solvay Conference
of Electrons and Photons (1927)

3rd Row: A.Piccard, E. Henriot, P. Ehrenfest, Th. De Donder, E. Schrodinger, J. E. Verschaffelt, W. Pauli, W. Heisenberg, R.H. Fowler, L. Brillouin;

2nd Row: P. Debye, M. Knudsen, W. L. Bragg, H.A. Kramers, P.A.M. Dirac, A. H. Compton, L. de Broglie, M. Born, N. Bohr;

1st Row: I. Langmuir, M. Curie, H. A. Lorentz, A. Einstein, P. Langevin, C.T.R. Wilson, O.W. Richardson
Hydrogen Atom Emission Spectrum
Relaxation of an excited H atom:
 A photon is emitted with the exact energy of the energy difference
between the initial and final states.

ΔE = Ei - Ef