Introduction to Atomic and

Molecular Theory
(Module Chemistry 212)

By
Tefera Entele
Book of the Power Point Slides
Please bring this book to all lectures

At the end of the book, you will

find tutorial problems. Your
answer to these questions must
be handed in to your Teacher
two days before each tutorial ( I
will tell you which problems to
attempt each week)
Recommended Textbooks
There are 2 books which are
helpful to you
Inorganic Chemistry by
Bowser
A concise Inorganic Chemistry
by J. D. Lee
Inorganic Chemistry By James
E. Huheey
 Atoms Greek philosophers pure
theory
Early nineteenth century-John Dalton-first scientific
basis
Early twentieth century- Electron Rutherford-
Nuclear atom (only 1/1850 of
mass)
For hydrogen (simplest atom)
Atomic radius ( 50 pm) Nucleus
(nearly all the mass, radius 10-3
pm)
Rutherford tried to use classical mechanics
(Newton to explain behavior of atoms)
He Failed
Need completely new principles-
quantum mechanics-developed
1900-30
Atoms, electrons etc. do not
behave like the every objects
that we can see.
Hard to visualise-so let us step back
and look at the behavior of
radiation (light)
In the late 19th century, everyone knew
that radiation consisted of travelling
WAVES (diffraction etc.)

Amplitude

Velocity of propagation = 3.00 x 108 ms-1

speed of light Number of vaves
passing per second = frequency (),
Unit of frequency = Hertz (Hz), or
cycle per second
Whole range of radiation =
Electromagnetic Spectrum
Here is part of this spectrum:
Wavelength (,m) (short)10-8 10-6 10-4
Frequency (Hz) 3x1016 3x1014 3x1012

X-ray Infrared

UV-Visible
The wave consists of an oscillating ELECTRIC
FIELD-moving at the velocity of light
 Note the relationship between
wavelength and frequency:

Short wave length, high

frequency

Long wave length, low frequency

= c Where c= velocity of
light
BUT in the late nineteenth century some problems appeared.
Several properties of radiation were discovered for which could
not be explained by waves. No time to go into detail about these,
but
Such problems were explained by Planck and
Einstein.
Planck and Einsteins explanation:
1. Radiation was quantised, i.e. consists of a stream
of PARTICLES.
2.These particles (quanta) are called PHOTONS.
3. The energy of quantum(photon) is given by the
equation
E = h
Where h = Plancks constant, 6.63 x 10-34 J s
There is therefore strong evidence that
radiation has the properties of both
waves and particles!!
All early experiments on atoms, nuclei and electrons
assumed that they were particles.
But no theory could be found to explain
their properties.
Then in 1922, the French Physicist de
Broglie made a novel suggestion-if light,
which every one knew was waves, could
behave like particles, perhaps electrons
etc., which every one knew were
particles, could also behave like waves.
The de Broglie
relationship
De Broglie pointed out that the energies calculated
for a wave and for a particle must be equal for any
thing that was behaving as both.

De Broglie showed that =

Where h/pand
= wavelength of wave,
p = momentum of particle
(i.e. mass x velocity)
h = Plancks constant
This important equation links together wave () and particle (p) properties.
The de Broglie relationship links particle
behavior (p) to wave behavior ()
He then proposed that electrons (and indeed
any particle) would obey the same
relationship.
Revolutionary proposal needs proof!
How to detect wave behavior? DIFFRACTION
Electron diffraction founded by two groups
almost simultineously in 1925/6 (Davisson and
Germer (U.S.) and G.P. Thomson (U.K)) Their
experiments showed de Broglie was absolutely
correct, and the wave associated with the
electrons had exactly the predicted
wavelengths.
The de Broglie relationship
applies to all particles, i.e. all
particles possess an associated
wave.
Why are we unaware of this for every
day object?
It is because the Plancks constant
(h) is so small
A ball (mass 100 g) travelling at 1 ms-
1 will have an associated 34
h
wavelength h of 6.63 10 J .s
p

mv
1 1
(10 kg ) 1m.s
= 6.63 x 10 -33
m
This wavelength is totally undetectable
Compare with an electron travelling at
3.5 x 105 m.s-1 which is 2.2 nm
This is now an easily measurable
amount, and not much larger than the
dimensions of atoms.
Thus we cannot ignore the wave
properties of an electron
The equation E = applies only to photons of
electromagnetic radiation (i.e light)
The de Broglie equation does not apply to photons
because they have no mass and their velocity is
constant.
Photons do display wave-particle duality (i.e. they
can seem to behave as particles or waves
depending on the experiment) but this duality
cannot be expressed by de Broglie equation.
All particles with mass (i.e. every thing except
photons) are subjected to the de Broglie equation
and therefore have Matter waves (not
electromagnetic waves) associated with them
The Uncertain Principle
Early ideas treaded the electrons in an atom
like planets going round the sun. The path
was a well-defined ORBIT.
Now that we know that an electron has
wave-like properties, with the same
order of magnitude as the size of an
atom-such precision is impossible.
All that we can do is to determine the
probability that an electron is in a
certain place.
This uncertainty was quantified by
HEISENBERG
In 1927, Heisenberg established his
UNCERTAINITY PRINCIPLE.
Suppose that the electron has a
position in space defined by 3
coordinates: x, y, z and has
momentum parallel to each axis: px,
py, pz
h
x.principle
The uncertainty p x states that
4
The more accurate we know the position of an electron,
the less accurately can we know its momentum, and
vice versa.
This is not due to our experimental inadequacy, it is an
inherent property of matter
Two more points about the Heisenberg Uncertainty
Principle:
1. It applies to all matter but is only significant for
very small objects (size of atoms/molecules)
2. We must describe the behavior of an electron in
terms of probabilities. The exact orbits must be
replaced by ORBITALS
We need to determine the possible orbitals for
electrons in atoms, i.e. the allowed probability
distributions
Wave Functions
How to describe the behavior of an
electron?
Replace well defined trajectory of a
particle by a wave function. This tells
us how probable it is that an electron
is at a particular