Quantum theory

and Atomic structure

CM1502
Chapter 1
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Light and Matter
All matter is made up of charged particles.
Accelerating charges emit and absorb
electromagnetic radiation (EMR).
EMR is characterized by its frequency, , and its
wavelength, .
Light (EMR) travels at a fixed speed, c.
There is a relationship between c, and .
= c
(1.1)
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The Wave
nature
of light
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Amplitude is the height
of the crest or the depth
of the trough of each
wave.
Amplitude is related to
the intensity of the
radiation which we
perceive as brightness in
the case of visible light.


The Wave nature of light
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Classical Distinction between
Wave and Particle
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Electromagnetic Spectrum
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Continuous Spectra
A warm solid, liquid and plasma will radiate at
all wavelengths thus producing a continuous
EM spectrum.
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Discrete Spectra 1
A warm gas emits EMR, but at certain specific
wavelengths thus producing a discrete EM
spectrum.
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Discrete Spectra 2
A gas can also absorb EMR and does so at
discrete wavelengths.
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Examples: Spectra of Stars
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Examples: Gas clouds in space 1
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Line spectra of Atoms
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Hydrogen Atom Spectrum 1
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Hydrogen Atom Spectrum 2
A high school maths teacher, Balmer, in 1885
noticed that the wavelengths of the visible lines of
Hs spectrum could be represented by the formula:
... 5 , 4 , 3 ,
1
4
1 1
2
H
=

= n
n
R

where R
H
is a constant.

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Hydrogen Atom Spectrum 3
Later Rydberg showed that all the H atoms absorption
and emission lines (not just those seen in the visible,
i.e., the Balmer series) could be represented by the
formula
where R
H
is, as before, a constant now known as the
Rydberg constant, 1/R
H
= 91.1763 nm.

... 3 , 2 , 1 ..., 3 , 2 , 1 ,
1 1 1
1 1 1 2 1
2
2
2
1
H
+ + + = =

= n n n n n
n n
R

(1.2)
The Rydberg equation and the value of the constant are
based on data rather than theory
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The Unexplained
Why do the spectral lines of Hydrogen appear in a
pattern?
Is there any importance about this experimental
observation?
Over a wide range of wavelengths, light is only
observed at certain discrete wavelengths
Light is quantized (?)
It was taught before that light behaves as wave
only


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Explaining Rydbergs Formula
Quantization of Light
Max Planck first proposed that light could be
quantized into little packets of energy.
The packets of energy, called photons, have an
energy value of,
h E =
(1.3)
where h is Plancks constant.

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Bohrs H atom 1
Bohr postulated that an atom could only exist in certain
allowed states of specific total energy E which he called
stationary states. Atoms do not leak energy while in one
of its stationary states.

If an atom was not in its lowest energy state (ground
state), then it could make a downward transition, to a
state of lower energy and in the process, emit a photon.

High energy atomic state = E
u

Low energy atomic state = E
l
.
E
u
E
l
= E = a photon energy = h.

Bohrs postulated fixed atomic states and energy levels
and this leads naturally to discrete spectra.
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The energy levels of hydrogenic
atoms/ions
E
n
=-2.18 x 10
-18
J Z
2
/n
2
The negative sign for the energy appears
because we define the zero point of the atoms
energy when the electron is completely
removed from the attraction of the nucleus
A table top analogy for defining the
energy of a system.
If you define the zero point of your
textbooks potential energy when the
book is on the table, the energy is
negative when it is on the floor.
2
2
2
0
4 2
1
8
n
h
e Z
E
n

=
(1.4)
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The lowest energy state of hydrogen atom n=1 has
the energy of -13.6eV or -1312 KJ/mole.

The amount of energy needed to promote an atom
from the ground state to a given excited state is
called excitation energy.

The amount of energy needed to remove an electron
from an atom in ground state is called the ionization
energy.

The separation energy is energy needed to remove
an electron from an atom in any excited state.


H Atom Energy States
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n=1
n=

n=5
n=4
n=3
n=2
-13.6/2
2
= -3.4 eV

-13.6/3
2
= -1.51eV

-13.6/4
2
=0.85eV

-13.6/5
2
=-0.54eV

0

-13.6eV

1
st
excited state
2
nd
excited state
Ground state
a
b
a: Ionization energy = +13.6eV
b: Excitation energy
c,d:Separation energies
Energy level diagram for hydrogen atom
c
d
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Applications of Bohrs equation for
energy levels of an atom
We can find the

-difference in energy between two levels.

-energy needed to ionize the H atom

-wavelength of the spectral line.

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Figure 7.11
The Bohr explanation of the three series of spectral lines.

E of emitted photon: UV series > VIS series > IR series
n in Rydberg equation
23
A spectral line results because a photon of specific energy is emitted.

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Limitations of Bohrs Model
Works only for hydrogenic species (one electron
species) such as H, He
+
, Li
2+
etc

Fails for atoms with more than one electron
because the e-e repulsions and additional nucleus
electron attractions create more complex
interactions.

He assumed that an atom has only certain energy
levels in order to explain line spectra. However he
has no theoretical base for the assumption.
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Louis de Broglie
considered other
systems that display
only certain allowed
motions such as the
vibrations of a plucked
guitar string.
He proposed that if
energy is particle-like,
perhaps matter is wave
like.
If electrons have
wavelike motion in
orbits of fixed radii, they
would have only certain
allowable frequencies
and energies.
de Broglie and Standing Waves
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Fundamental or 1
st
Harmonic
2
nd
Harmonic or 1
st
Overtone 3
rd
Harmonic or 2
nd
Overtone
Animations of standing waves
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Perhaps the electrons, fixed to occupy specific orbits,
behaved like standing waves?
Took the formulae E = mc
2
and set it equal to E = hc/
to obtain for a photon = h/mc, m is equivalent
mass (not actual) of a photon.
For a particle, he substituted v (velocity of the particle)
for c.
de Broglies Matter Waves
mv
h
=
particle

(1.5)
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Electrons were shown by G.P. Thomson
to diffract!
Only waves diffract!
de Broglie proposed that the circular
orbits of electrons were actually
standing-waves.
Bohrs orbits were the paths around
which the wave may vibrate.
Only certain orbits fulfill the standing-
wave condition, i.e., that an integral
number of wavelengths fit into the
circumference of the orbit.
That is, 2r = n
electron
a major application of electron travelling
in waves is the electron microscope
Particles Act Like Waves!
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x-ray diffraction of
aluminum foil
electron diffraction of
aluminum foil
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Light and matter can interact.
Light can be absorbed and emitted by matter.
The absorption and emission can be continuous or
discrete.
Light is quantized, E = h.
The energy states of atoms (and molecules) are
quantized.
Discrete spectra can be explained by atoms
undergoing a transition and emitting or absorbing a
photon of energy.
Matter has wave properties.
The energy stationary-states of hydrogenic atoms
(only) can be explained by electrons existing in
standing-waves that surround the nucleus.
Summary
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Here is all about the
new postulate of de
Broglie regarding
matter-waves
Matter waves..
If they are
waves, they
must obey a
wave-equation!

Prof., Erwin Schrdinger
physical chemist Peter Debye
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The Schrdinger Wave Equation
Schrdinger eventually came up with the famous equation:
is the total energy operator or Hamiltonian operator. It
represents a set of mathematical operations that when
carried out with a particular wave function, yields one of the
allowed energy states of the atom. Thus each solution of
the equation gives an energy state associated with a given
atomic orbital.
is the wave function also a mathematical function.
E is the total energy of the system under consideration it
is simply a number with units of J .
n n n
E H =

(1.6)
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The Wave Function,
is just a function, like x
2
, or sin x, or e
x
.
This function depends on the positions of all the
particles in the system under consideration.
For the hydrogen atom, it is a mathematical function of
the position of the electron and proton.
If we were looking at H
2
O instead, then is a function
of the positions of the two H nuclei, and the O nucleus
and the positions of each and every one of the 10
electrons.
For each value of n we have, we will have a different
n
.

That is,
1
,
2
,
3
etc.
Later we will see that these are the 1s, 2s, 3s, 2p and 3d etc. atomic
orbitals.

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Solving the Schrdinger Equation
Solving the Schrdinger, therefore, involves finding the
correct mathematical function such that when we operate on
that function with we get a constant times the original
function back again.

If we can do this then the constant is the energy of the
system.

Upon solving the Schrdinger equation it was found
thatthree integers, denoted as n, l, m
l
fully characterized
the functions that solved the Schrdinger equation.
(According to Bohr, only n was needed)



( ) ( ) ( ) , , ,
, , , ,
l l
m l l n m l n
Y r R r =
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The Total Energy, E
n


Interestingly, the formula for the energies was the same as derived
from the Bohr and Bohr-de Broglie models, and did not depend on l,
nor m
l
.




Recall that E
n
represented the energy of the H atom when its electron
was in orbit number n.









Thus the n here reminds us that our system, here the H atom, could
exist in any number of energy states.
Each energy state being labeled by n, with the lowest being n = 1.
2
2
2
0
4 2
1
8
n
h
e Z
E
n

=
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one electron
system
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Quantum Numbers n, l, and m
l

n the principal quantum number (QN). The energy of
hydrogenic atoms depends only on this quantum
number.
Can take the values 1, 2, 3,

l azimuthal QN, or orbital angular momentum QN. Is
associated with the allowed angular momentum of an
electron in an orbital.
Can take the values, 0, 1, 2, , (n - 1)

m
l
magnetic QN, or orbital angular momentum
projection QN. Is associated with the orientation of the
orbital angular momentum
Can take the values, -l, -(l-1), -(l-2), , 0, 1, 2, , l, i.e., m
l
goes
from l to l in steps of one.
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Allowed Values of the Quantum
Numbers
Will denote here as (n, l, m
l
)
Some allowed values:
(1,0,0), (5,4,-1), (2,1,0), (2,0,0),
(4,3,3)
Some impossible values:
(1,1,0), (5,4,-5), (2,1,-2), (2,0,1),
(0,3,3), (0,0,0)
By convention lower-case
letters have been used to
designate the l QN.
l Letter
0 s
1 p
2 d
3 f
4 g
5 h
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Another Way
At around the same time Schrdinger developed the
matter wave equation, another scientist was
formulating quantum mechanics in an entirely different
way.

Heisenberg used linear algebra, or matrix algebra, and
developed quantum matrix mechanics.

A very important, finding from this approach is
Heisenberg Uncertainty Principle.
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Heisenberg Uncertainty Principle
Heisenberg uncertainty principle states that it is
impossible to know simultaneously the position
and momentum of a particle.
p . q
h
4
where
q = uncertainty in position
p = uncertainty in momentum
h = planks constant
m = mass of the particle


p = m.u
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The Heisenberg Uncertainty Principle
Because energy is directly related to p, what the
uncertainty principle means for us is that because
the energy of an atom is known with considerable
accuracy, the location of the electron within the atom
is not known at all, accurately.

This means that nice circular orbits of electrons
around nuclei can not be correct.

Worse is that electron positions can only ever be
known in terms of probabilities rather than assigning
to them a special spot around the atom.
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The Probable Location of the electron
While we cannot know the exact
position of the electron, we can know
where it probably is. i.e. where it
spends most of its time.


2
is called the probability density, a
measure of probability of finding the
electron in some tiny volume of the
atom.

Electron probability density in the
ground state H-atom is shown in the
figure.

The probability density decreases
with r but does not reach zero.

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Radial probability distribution
The total probability of finding the electron at
some distance r from the nucleus is called
radial probability distribution.
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Probability Density vs Radial
Probability Density (RDF)
Dartboard analogy to a 1s orbital.
Imagine that a single dart (electron)
is thrown at a dartboard 1500 times.
The board contains 90% of all the
holes; it is analogous to the 1s
orbital. Where is a thrown dart most
likely to hit? The number of holes per
unit area is greatest in the 50
region-that is, the 50 region has the
greatest probability density. The
most likely score is 30, however.
Even though the density of holes is
not as great, the total area, and
hence the total number of hits, is
greater in the 30 ring than in the
50 ring. The probability of scoring
30 is greater than that of scoring
50.
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Analyzing the Dart Board
Zone N
holes
Area
holes
Prob %
50 169 3.14 53.79 11
40 358 9.42 37.98 24
30 401 15.71 25.53 27
20 268 21.99 12.19 18
10 154 28.27 5.45 10
Probability per unit area is
highest in the 50 zone
2

Most likely place to find
a dart, however, is in
the 30 zone RDF
Not as many holes per unit area as,
but a lot more places for the holes to go.
Even more places for the holes to go, but far
too few holes per unit area
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Shape of s orbitals
An orbital with l=0
has
a spherical shape
with the nucleus at
its centre is called s
orbital. Because a
sphere has only one
orientation, an s
orbital has only one
m
l
value.

Node is the region
where the probability
of finding the
electron drops to
zero.
( )
0
/ 2 / 3
0 0 , 0 , 1
1
, ,
a r
e a r

=

( )
0
2 /
0
2 / 3
0 0 , 0 , 2
2
2 4
1
, ,
a r
e
a
r
a r

3,0,0
(r,,) =
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Shape of 2p orbital
An orbital with l=1 is called p orbital and
has two regions of high probability, one
on the either side of the nucleus.
there are three possible ml values
M
l
=-1,0,+1. Hence three possible
orientations in mutually perpendicular
directions.
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Shape of 3d orbital
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Shape of orbitals with higher l values
Orbitals with l=3 are f orbitals.
They have 7 orientations.
Given figure shows one of the seven
orientations.
What does an h orbital look like?
Check out these site:
http://www.orbitals.com/orb/orbtable.htm
http://winter.group.shef.ac.uk/orbitron/
J ust for interest
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Radial Distribution
Functions/Bohrs radius
Note the probability maxima
occurs at the same orbit
radius fixed by Bohr

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Radial Distribution Functions
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Summary
Atomic orbitals are solutions to the Schrdinger equation
for hydrogenic atoms.
Atomic orbitals are characterized by three quantum
numbers (QN).
n the principal QN and ranges from 1 up to infinity. The larger
the n, the more extended the orbital.
l the orbital angular momentum QN, and ranges from 0 up to n-1.
l gives the shape of the orbital.
l = 0 is an s orbital, l = 1 is a p orbital, l = 2 is a d orbital, etc.
m
l
the orbital angular momentum projection QN, and ranges from
l up to l in steps of 1. m
l
gives the orientation of the orbital.

2
is the probability density of finding the electron at
position (r,,) or (x,y,z).
The radial distribution function gives the probability
density of finding the electron at a distance r from the
nucleus, regardless of direction.
We finally arrive at the shapes of different atomic
orbitals.
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