Quantum Mechanics

Physical Chemistry II
Bonding and Symmetry
Quantum Theory
Quantum Theory
At the end of the 19th century
there were three experimental
results that could not be
explained by classical mechanics.
It was necessary to introduce a
new theory called quantum
theory (quantum = a discrete
amount).
The first of our problems with
classical mechanics arrives when
we consider blackbody
radiation (BBR).
Sir. Isaac Newton

2
Blackbody Radiation
An ideal blackbody absorbs
electromagnetic radiation of all
frequencies.
When heated, the radiation
emitted from the blackbody is
independent of its material and is
only dependent on its
temperature.
A hot body gives off radiation
because its electrons/atoms are
in motion.
Sir. Isaac Newton
3
Blackbody Radiation
Experimentally it is found that
the intensity of BBR varies with
the wavelength of the emitted
light.
As the wavelength ()
decreases, the intensity (I)
increases.
The wavelength of the light
emitted at greatest intensity is
denoted: max.
As the temperature increases, the intensity of light
emitted increases and as such max moves to lower
wavelengths.
Blackbody Radiation
Wiens displacement law
(Wiens law).
T is the temperature in K.
b is Wiens displacement
constant:
2.897 768 5(51) 103m K
Stefans Law: The total energy
density (power emitted/
brightness) is proportional to T4.
Wilhelm Carl Werner Otto

Fritz Franz Wien
5
How come infrared satellites

can see me in a building?
Wiens displacement law (Wiens law).
T of me = 310 K
T of building = 298 K
b = 2.897 768 5(51) 10-3 m K
Near-infrared (NIR): 0.75 - 1.4 m
Short-wavelength infrared (SWIR): 1.4 - 3
m
Mid-wavelength infrared (MWIR): 3 - 8 m
Long-wavelength
(LWIR): 8 - 15 m
Far infrared (FIR):infrared
15 - 1000
6
Blackbody Radiation - The

problem...
So what was wrong with classical
mechanics?
In classical mechanics our solids
are composed of atoms which are
bound together by forces which
we can think of as a spring.
Therefore, in classical
mechanics, once a solid is excited
(by radiation) all the springs
should oscillate.
7
Blackbody Radiation - The problem...

Rayleigh and Jeans: the
contribution to the energy density
from electromagnetic radiation
in the range
is:
where
This works fine for long
wavelengths, but as we get to
shorter and shorter values
the energy output
approaches infinity. This is
known as the ultraviolet
Plancks Solution
Max Planck proposed:
A hot glowing body could emit or
absorb certain quantities of
energy given by the equation:
E = energy of the radiation

n = +ve integer
h = Plancks constant
v = frequency
Max Planck
9
Plancks Solution
Max Planck proposed:
The oscillating atomic particles in
the BB could only have certain
vibrational energy levels. This led
to:
This gives very good

agreement with experiment.
Max
Planck
10
Plancks Solution
When
is long, we can replace

by the series:
Therefore, at long wavelengths:
Collapses to Rayleigh-Jeans
Classical Formula.
Max
Planck
11
Plancks theory for BBR!

Plancks theory states that oscillators are excited if and
only if they can acquire an energy of nhv.
This energy may be too large for the case of very high
frequency oscillators and so they remain unexcited.
The effect of quantisation is to reduce the contribution
from the high frequency oscillators.
12
The Photoelectric Effect

The second experiment in our list
of three that exposes a few
shortcomings of classical
mechanics.
A beam of light shining onto a metal
surface can eject electrons. The
emission of electrons shows an
interesting dependence on the
frequency (v) and the intensity (I)
of the light:
Regardless of the light intensity no electrons are emitted until the
frequency exceeds a threshold value, vo.
The electrons are emitted the moment the light (with v vo) hits the
surface, regardless of the intensity of the light - there is no time
lag.
13
So... Why is this strange?

In classical mechanics, light is
thought of as a wave (recall Thomas
Young and his famous Double-slit
experiment - Newton believed light
was a particle).
14
Double Slit Experiment
15
So... Why is this strange?

In classical mechanics, light is
thought of as a wave (recall Thomas
Young and his famous Double-slit
experiment - Newton believed light
was a particle).
Recap - Wave Theory of Light
The energy of the light depends on the amplitude (i.e.,
the intensity) of the wave and not on the frequency.
16
Problems: Wave Theory of Light.

The energy of the light depends on the amplitude (i.e.,
the intensity) of the wave and not on the frequency.
Thus, one expects that an electron will break free from
the metal surface when it has absorbed enough energy
from the light of any frequency.
In dim light there would be a time-lag before the
electron would be emitted as the electron would have
to absorb enough energy to break free.
17
Einsteins Solution
Einstein proposed:
That light consists of packets of
energy related to the
frequency by:
The intensity is related to the
number of photons striking the
surface not their energy.
That an electron in the metal
absorbs a photon and the energy
is transferred entirely to the
electron.
Albert Einstein
18
Einsteins theory for PEE!

A photon of a certain minimum
energy must be absorbed for an
electron to be freed (i.e., to
overcome the attractive forces
holding it to the metal).
This energy is known as the
binding energy - or alternatively
one could call it the work
function (W).
The number of electrons emitted in dim light is smaller than the

number emitted in bright light because fewer photons are
present in the dim light.
As long as the dim light is of sufficient energy (vo) the electron
will be expelled the instant the light hits the surface: no time-lag. 19
Einsteins theory for PEE!

The photoelectric effect led to the view that light
consists of photons that behave like particles.
However, light behaves as a wave (e.g.,
diffraction)
This led to the concept of the dual nature of light
known as wave-particle duality.
When light is in motion - use the wave model.
When light is interacting with matter - use the particle
model.
29
Atomic Emission Spectra.

When an electric current is passed through hydrogen
gas, at low pressure, light is emitted.
The light consists of a series of lines, which converge
towards the high frequency end of the series.
21

The series are named after the discoverer:
Lyman series in the u.v. region.
Balmer series in the visible region.
Paschen series in the infrared region.
The wavelengths of the lines are given by:
In the Lyman series: a=1, b=2,3,4,...

In the Balmer series: a=2, b=3,4,5,...
In the Paschen series: a=3, b=4,5,6,...
22

The line emission spectrum (LES) of atomic hydrogen
was very puzzling for the early spectroscopists.
Why would an atom emit only certain frequencies of
light and not all possible frequencies?
The answer must be that an atom can only lose energy
in certain discrete amounts...
23
The Bohr Theory (of Hydrogen).

Three Postulates!
The electron in the hydrogen atom
can only move in certain fixed
circular orbits. It does not radiate
energy while in these orbits.
Therefore, the orbits are called
stationary states.
Associated with each of these states
is an energy level. The electron can
move to another orbit only by
absorbing or emitting a photon whose
energy equals the difference
between the two energy levels.
Niels Bohr
24

Associated with each orbit is a
quantum number n.
n can have values 1,2,3,...
The radius of the orbit is
proportional to
n2
The energy of an orbit is

proportional to
-1/n2.
Niels Bohr
25

The lowest energy level occurs at the
n=1 orbit.
When the electron is in this orbit the
hydrogen atom is said to be in the
ground state.
When the electron is in a higher
orbit, that atom is said to be in an
excited state.
Niels Bohr
26
The LES of hydrogen (Bohr).

When hydrogen is subjected to
electric discharge, the added
energy causes an electron to jump
to an excited state.
The excited atom is unstable and
the electron returns to a lower
energy level, accompanied by an
emission of an amount of
energy equal to the energy
difference between the higher
and lower energy level.
As the energies of the orbits are
quantized, the amount of energy
is also quantized.
27
The LES of hydrogen (Bohr).

The Lyman series results
when the electron returns
to the n=1 level.
The Balmer series results
when the electron returns
to the n=2 level.
The Paschen series results
when the electron
returns to the n=3 level.
28
Bohrs Theory.
The Good Stuff.
The idea that only certain energy levels are possible.
The energy levels are described by quantum numbers
that can have only certain allowed values.
The Maybe Not So Good Stuff.

- It can not predict the energy levels and spectra of
many-electron atoms (i.e., anything bigger than
hydrogen).
- Electrons do not move in fixed circular orbits.
29
De Broglie Equation.
If light can behave in some
respect like matter, then perhaps
matter can behave in some
respects like light.
That is both light and matter
have wave-like as well as
particle-like properties.
De Broglie used two equations to
formalise this idea.
Louis-Victor-PierreRaymond, 7th duc de
Broglie
30
De Broglie Equation.
So De Broglie suggested that a
similar equation could be applied
to an electron instead of a
photon - i.e., we simply replace
the speed of light (c), by the
speed of an electron (v).
The resulting equation allows the
calculation of the wavelength of
any moving particle via:
Louis-Victor-PierreRaymond, 7th duc de
Broglie
31
Wavelengths of Objects
What is the wavelength of:
A cricket ball (0.142 kg) moving at 25 ms-1?
An -particle (6.6 x 10-27 kg) moving at 1.5 x 107 ms-1 ?
32
The wavelength of an electron.
An electron of mass 9 x 10-31 kg

moving at 5.9 x 106 ms-1 has a
wavelength of 1 x 10-10 m.
Now if particles do behave like

waves then we should be able to
see their diffraction pattern
(remember the Double-slit
experiment!)
Waves exhibit a diffraction

pattern via:
33
The wavelength of an electron.

As an electron has a wavelength of 1 x 10-10 m, then to
produce a measurable value of , then d and should be
of the same order.
It so happens that the distance between
ions in a crystal is 1 x 10-10 m.
The Davisson-Germer experiment - A
diffraction pattern was obtained and
calculated from the experiment was
equal to the value predicted by De
Broglie using the wave-particle duality
theory.
Thus, the De Broglie relationship is
true.
34
Heisenberg Uncertainty Principle.

In the macroscopic world, a moving particle has a
definite location at any instant.
The position and the momentum of the object are
defined by taking snapshots of it at different times.
Thus photons must be scattered from the object.
Furthermore, this implies that the photons will not alter
the trajectory of the object.
In the microscopic world, the scattering of a photon
used in determining the momentum of a microscopic
object (an electron) will alter the objects trajectory.
Furthermore, if we tried to determine the position of an
electron, the interaction between the electron and the
measuring device would alter its momentum.
35

So we cannot make simultaneously precise measurements
of both the momentum and position of a particle.
It is impossible to know simultaneously the exact position
and momentum of a particle.
The more precisely we know the position of the particle,

the less precisely we know the momentum (velocity)
vice
and versa.
36

Example.
An electron has a speed of 6 x 106 ms-1 with an uncertainty of 1%.
What is the uncertainty in the position of the electron?
The diameter of the atom is of the order 10-10 m. Therefore, we have no

precise idea where in the atom the electron is located. Hence we talk
about probabilities of an electron being at a particular place at some
particular time.
37
Wavefunctions
From De Broglies work, it seemed logical that an
electron with wave-like properties should be described
by a wavefunction .
irectly - just as in
We have no way of measuring d
classical optics there is no direct way to measure the
amplitudes of the electric and magnetic fields that
constitute the light wave.
However, the intensity of a light wave can be measured;
and the intensity is proportional to the square of the
amplitude of the electric field.
38
Wavefunctions
The intensity is proportional to the density of photons
at that point in space. That is, to the probability
density of finding a photon there.
We can interpret 2 as a probability density and to
calculate the probability that the particle is in a small
region of space, we multiply 2, by the volume of the
region, V.
Example:
if 2 = 0.1 pm-3 at a point.
and V = 2.0 pm3.
Then the probability of finding the particle at that specific point is
0.1 x 2.0 = 0.2.
39
Wavefunctions
If we add together the probabilities at every point in
space, then the total probability of finding the particle
is 1.0. This is expressed mathematically as:
When this occurs the wavefunction is said to be

normalised.
40
Foundations of Quantum Theory
The foundations are based on two postulates.
Consider a system of n particles which could be

described classically by specifying 3n coordinates
(q1...q3n) and 3n momenta (p1...p3n).
41
Foundations of Quantum Theory

Postulate 1.
The system can be described by a wavefunction:
This contains all there is to know about the system, all

the experimental values can be found from .
The variable t stands for time (ignore this!).
What are the conditions for the wavefunction () to
be
acceptable?
42
Postulate 1. Conditions on .
is interpreted physically by:
This is the probability of finding the n particles with
coordinates lying between q1...q3n and (q1+dq1)...(q3n
+dq3n).
Since each particle must be somewhere in space, we
have the normalisation condition:
There are four further conditions to the normalisation

condition that the wavefunction must satisfy in order
to be physically acceptable.
43
Postulate 1. Conditions on .
The wavefunction must be:
1. Single-valued (strictly, *
should be single-valued).
2. Not infinite over a finite
range.
3. Continuous everywhere.
4. Possess a continuous first
derivative.
44
These conditions imply that there are

only certain allowed wavefunctions.
Now in order to extract information
from our wavefunction we will need to
do something to it.
We need to operate on it...
45
Postulate 2.
Every observable ( ) is represented in quantum theory by an
operator -
There are two ways we can obtain the value of the

observable.
(i) Find the exact value of the observable. That is:
(operator)(function) = (numerical value)(function).
-
Example: operator =
function =
func@
on
operat
valu
46
Postulate 2.
Thus for the wavefunction we will use:
(operator)(wavefunction) = (observable)(wavefunction).
This is known as an EIGENVALUE equation, where o is the

eigenvalue and is the eigenfunction.
47
Postulate 2.
(ii) The second means of extracting information is to find
the average value of the observable - also known as the
expectation value.
In order to obtain a quantum mechanical operator, one

must first obtain the classical expression for the
observable in terms of:
(a) the coordinates (q1...q3n)
(b) the momenta (p1...p3n)
For the n particles.
48
Operators.
The quantum mechanical operator is obtained from the
classical expression by:
(a) leaving alone the terms containing the
coordinates.
(b) replacing each cartesian component of pk

(where k = x,y,z) with:
49
Operators.
In this course we are concerned with the energy, E, as the
observable. The energy operator is known as the
Hamiltonian,
The equations using the Hamiltonian are known as
the
Schrdinger Equations.
50
Hamiltonian Operators.
The classical energy expression for the hydrogen atoms is:
0 Kine
@c
Energ
y
Coulo
mb
Poten
@al
Energy
vacuum
permi@vi
ty
Note: if the charges have the same sign, then the

coulomb potential energy is positive and therefore
repulsive.
if the charges have opposite signs, then the
coulomb potential energy is negative and therefore
attractive.
51
0 Kine
@c
Energ
y
The kinetic energy terms are

containing momenta via:
Now:
Coulo
vacuum
mb
permi@vi
Poten
ty
@al
Energy into terms
converted
And recall i2=-1.

So we can write the
kinetic energy terms as...
52
Laplacian function
Hence the Hamiltonian operator is:
53
Particle in a One-Dimensional Box

The classic case.
Here, we have a particle (e.g., an
electron) which is confined to a onedimensional (1-D) box of length a.
The potential energy (V) is zero
within the box and infinite outside
of it.
a) The Hamiltonian Operator for the particle in a 1-D box
is derived from the energy expression:
KE
PE
54

Translate KE into a QM operator.
The Schrdinger Equation is:
Which, for our 1-D box, yields:
55

b)
Solution of this equation.
This is a second-order differential

equation and the general solution is:
A, B, and k, are constants. Therefore:
56
57

c)
Values for the constants k, A, and B.
Since the potential outside the box is

infinite, the wavefunction does not
extend beyond the box. Therefore, we
obtain the boundary conditions:
Applying the boundary conditions to the wavefunction:
x=0:
58

x=a:
So, either A=0, or sin(ka)=0.

If A=0, then the particle does not exist anywhere in
the box. Thus, sin(ka)=0.
This leads to the condition:
Plugging this back into our equation for the energy,

yields:
59
Thus, we see that the energy levels of the particle

in the box are quantized. n, are quantum
numbers and these label the wavefunctions n and
the energies En.
So we have k, and B, what about A.
We know that the particle must
exist somewhere in the box. So,
from the normalisation condition
of the wavefunction:
60
61
Where: n=1,2,3,...
There is no 0.
Putting n=0 in n would mean 0 is zero everywhere
in the box.
This would also mean that 0 2 would be zero
everywhere and therefore there could not be a
particle in the box.
62
Particle in a 1-D Box Wavefunctions

Each wavefunction is a standing wave - like a guitar
string which is fixed at both ends - it can vibrate in
only a restricted set of ways.
As the energy increases, the
number of nodes present (n-1)
increases.
The most probable position for a
particle on the n=1 is in the
centre of the box. The probability
density (2) at x=a/2 is:
63
Particle in a 1-D Box Wavefunctions

In the n=2 level, there are two most
probable positions. At both x=a/4 and
at x=3a/4 the probability density is 2/a.
When n is large there are many
probable positions for finding a particle
and we approach the uniform
distribution predicted by classical
mechanics.
Thus, classical mechanics emerges from
quantum mechanics as high quantum
numbers are reached. This fact is
known as the correspondence principle.
64
Particle in a 1-D Box - Energies

The lowest energy state is E1.
E1 is called the zero point energy and it is entirely kinetic energy.
At the absolute zero of temperature, classical kinetic theory
predicts that all motion ceases. However, a finite quantity of
energy does remain. Thus, the lowest energy state is referred to
as the zero point energy.
The lowest energy state must be greater than zero in order that
we do not violate the Heisenberg Uncertainty Principle.
If the particle was stationary - i.e., zero kinetic energy both the energy (momentum) and the position would be
known exactly.
Example.
Calculation of E1 for an electron
in a 1-D box of length 2 (2x10-10
-31
Mass of an electron is: 9.11x10 kg.
6
5
Example continued...
So what if we want the energy of E2 or E3?
66

The energy levels (and therefore the
separations between them) are inversely
proportional to ma2.
If the particles are heavy, or if the box is large, then the
energy levels are close together and the system
behaves classically, with no observable quantisation.
Example: Calculate E1 and E2 for a ball (1 g) confined to a 1-D box
of length 1 m.
This energy difference is too

small to be measured
experimentally!
67

Example continued... The wavelength corresponding to a
transition between the E2 and E1 levels is:
This wavelength is difficult to

measure and so no quantisation is
detected.
For the earlier example of our electron in the 2 box, the
corresponding transition has a wavelength of 4.4 x 10-8 m.
68
Orthogonality of Wavefunctions
The orthogonality of wavefunctions implies that the overlap

of the wavefunctions n and m is zero.
The overlap is represented mathematically by:
For the one dimensional box, it is straightforward to derive

the orthogonality of the wavefunctions.
69
Orthogonality of Wavefunctions
So if we integrate over the entire length of our 1-D box:
70
Particle in a 2-D box.

Inside the box V=0, outside the box V=.
Square box (x and y directions) of length a.
The quantum numbers n and m are non-zero positive

integers, which arise from the boundary conditions in the
two dimensions.
1,2 and 2,1 have the same energy:
These energy levels are thus degenerate.
71
Particle in a 2-D box - Energy Level

Diagram.
72
Particle in a 3-D box.

The energy levels for a particle in a hollow cubical box
are given by:
The quantum numbers n, m and l are non-zero positive

integers, which arise from the boundary conditions in
three dimensions.
73
Particle in a 3-D box - Energy Level

Diagram.
74
Hydrogen atom.
a)
Treat as an isolated atom.

- We separate the motion (kinetic energy terms) of the whole
atom, from the motion of the electron relative to the nucleus.
- In order to do this we use the concept of the reduced mass of
the system .
Translation of the
system through
space - not
important - discard
K.E. of the
system important dont discard
75
Hydrogen atom.
The Hamiltonian of the Hydrogen atom is thus
reduced to:
b)
Use polar coordinates.

- As an atom is spherically symmetric it is convenient to use
polar coordinates instead of cartesian coordinates.
- Thus the wavefunction , needs to be expressed as:
76
Spherical Polar Coordinates.

We consider only one particle (the
electron) and consider its position (P)
relative to the nucleus.
r : distance of the electron from the nucleus.
: angle of r with the z-axis.
: angle of projection of r on the xy-plane,
relative to the x-axis.
The inter-relationships are:
77
The limits of integration are:
The polar form of the Schrdinger

equation allows us to separate (r,,)
into:
Radial
function
Angular
function
This will yield an equation where:

I. L.H.S. we have a function of r.
II. R.H.S. we have functions of and .
III.Both sides are equal to a constant.
78
Both functions are solved subject to

boundary conditions:
1.
R(r)0 as r
Y(,) is unchanged when:

1.
+2
2.
+2
Point (1) ensures that the electron is bound

to the nucleus.
Points (2) and (3) ensure that the angular

function is single-valued.
79
The Radial Function.

Radial functions have the general form:
Normalising x
constant
The first term (the normalising
constant) contains the quantum
numbers n and l. Normalises
the function.
For the term to survive:
a) n must be a positive
integer
b) l can have values from 0
Polynomial x
in r
Exponential
term in r
The second term contains a

polynomial in r and determines:
a) The value of R(r) at r=0.
b) The number of nodes
(R(r)=0).
80

2.0
Orbital Rnl(r)
1s
(Z/a0)3/2 . 2 . e-/2
1.5
1s
R [(Z/a0)3/2]
1.0
0.5
Z is the atomic number.

a0 is the Bohr radius = 52.9 pm.
0
0
10
15
The exponential term ensures

that R(r) 0 as r.
As n increases this function
does not decrease as quickly.
81

0.8
Orbital Rnl(r)
1s
(Z/a0)3/2 . 2 .
2s
(Z/a0) (1/8)
3/2
e-/2
1/2
. (2-) .
e-/2
When r=0 ( =0, i.e., at the nucleus)

the s-functions are non-zero.
For the 2s function, when =2 the R(r)
will be zero. There is one node
present.
A node is present when the function
passes through zero.
2
s
R [(Z/a0)3/2]
-0.2
0
10
15
82

0.4
Orbital Rnl(r)
1s
(Z/a0)3/2 . 2 .
e-/2
2s
(Z/a0) (1/8)
3s
(Z/a0)3/2(1/243)1/2 . (6-6+2) .
3/2
1/2
. (2-) .
3
s
R [(Z/a0)3/2]
e-/2
e-/2
-0.1
0
10
15
For the 3s function, there are two nodes

present.
Each function has (n l 1) nodes.
83

0.16
Orbital Rnl(r)
1s
(Z/a0)3/2 . 2 .
2s
(Z/a0) (1/8)
2p
(Z/a0)3/2(1/24)1/2 . () .
3s
(Z/a0)3/2(1/243)1/2 . (6-6+2) .
3/2
e-/2
1/2
. (2-) .
2p
e-/2
R [(Z/a0)3/2]
e-/2
e-/2
0
0
5
10
15
When =0, the p-functions are zero.

The 2p function has no nodes (2 1 1).
84

0.10
Orbital Rnl(r)
1s
(Z/a0)3/2 . 2 .
2s
(Z/a0)3/2(1/8)1/2 . (2-) .
2p
(Z/a0)3/2(1/24)1/2 . () .
3s
(Z/a0)3/2(1/243)1/2 . (6-6+2) .
3p
(Z/a0) (1/486)
3/2
e-/2
1/2
R [(Z/a0)3/2]
e-/2
3
p
e-/2
. (4-2) .
e-/2
-0.05
0
10
15
e-/2
The 3p function has one node.
85

0.05
Orbital Rnl(r)
1s
(Z/a0)3/2 . 2 .
2s
(Z/a0)3/2(1/8)1/2 . (2-) .
2p
(Z/a0)3/2(1/24)1/2 . () .
3s
(Z/a0)3/2(1/243)1/2 . (6-6+2) .
3p
(Z/a0) (1/486)
3d
(Z/a0)3/2(1/2430)1/2 . (2) .
3/2
e-/2
1/2
3d
R [(Z/a0)3/2]
e-/2
e-/2
. (4-2) .
e-/2
0
0
5
10
15
e-/2
e-/2
When =0, the d-functions are zero.

The 3d function has no nodes (3 2 1).
86
The Radial Distribution Function.

The square of the wave function gives the probability
density of finding the electron in a small volume at
a distance r from the nucleus.
However, if we want to evaluate the probable amount of
electron density on the surface of a sphere of radius r the angular function component of the wavefunction is
normalised. That is:
Radial
Distribution
Function
87
The Radial Distribution Function.
Among functions with the same principle quantum

number (n), those with smaller angular momentum
quantum number (l) have the greater probability of
having electron density close to the nucleus.
However, their principal maximum is further away.
88
Angular Functions Y(,)

Angular functions have the general form of:
Normalising x Polynomial in x Exponential
constant
cos/sin
in
As in the radial function, the first term contains the
quantum numbers which normalise the function.
The angular function is dependent on the quantum
numbers l and m.
The two quantum numbers are related in that m can
only assume values from -l 0 l.
n is not present in Y, therefore the angular function is
the same for all orbitals which differ only by the
principle quantum number (e.g., 1s, 2s, 3s... all have
the same angular function).
89
s Angular Functions (l=0, m=0)
There is no angular dependence for the s angular

function.
For every value of and , Y00 has the same
value.
The s angular functions are spherical.
90
p Angular Functions (l=1, m=-1,0,1)
Y1-1 and Y11 contain i and so we can not plot pictures of

these functions in real space.
We can obtain functions, which are equally valid solutions,
by taking a linear combination of the spherical harmonics
that have the same l.
Through the linear combination of the complex functions
91
we obtain real functions.
Now recall that: x = r sin cos : The above is px
Now recall that: y = r sin sin :The above is py

Also, as z = r cos : The Y10 function is pz
We can plot the functions in order to see what the
orbitals will look like. Consider pz where the only
angular dependence is on cos .
92
Plotting the pz function.

This is done as a polar plot, the value of cos is plotted
along a line which makes an angle of (to the z-axis).
The distance is measured irrespective of the sign, but the
function is said to be positive (+ve) or negative (-ve).
93

94

95

96

The plot is the same for every angle about the xy-plane.
Thus, we get two spheres that are joined at the nucleus.
The upper sphere represents the +ve part of the function
for =090.
The lower sphere represents the ve part of the function
for =90180.
97

The plot is the same for every angle about the xy-plane.
Thus, we get two spheres that are joined at the nucleus.
The upper sphere represents the +ve part of the function
for =090.
The lower sphere represents the ve part of the function
for =90180.
There is one nodal planes present at
=90. In s-angular functions there are
no nodal planes. In d-angular
functions there are two nodal planes
present.
The number of nodal planes in an
angular function is given by l.
98

If the functions px and py were plotted (by taking a series
of values of and ) we would obtain a 3-D graph,
identical in shape and size to that of the pz graph.
99
Interpretation of Angular Functions
Recall, that a wavefunction can be correlated

with physical reality through the square of the
wavefunction.
(Ylm)2 gives the probability of finding the
electron in a certain direction (that is, for
certain values of and ).
Therefore, the interpretation of Ylm is that the
square of the length on a polar diagram is
proportional to the probability of finding
the electron in that direction.
For the pz orbital the most probable direction is
along the +ve or ve z-axis, as pz has its largest
value in those directions.
Ylm
cos
cos2
1.00
1.00
30
0.87
0.75
60
0.50
0.25
90
0.00
0.00
120
-0.50
0.25
150
-0.87
0.75
180
-1.00
1.00
100
d Angular Functions (l=2,m=-2,-1,0,1,2)

For m=-2,-1,1,2 we have complex terms, similar to the
Y1-1 and Y11 functions, i.e., they contain emi.
In the same way as the p-functions we use a linear
combination of the complex functions to obtain real
functions.
101
102
103
Plotting the dz function.

2
The d angular functions are plotted

in a similar manner to the p
2
angular functions. Consider
dz
3 cos2-1
2.00
30
1.25
60
-0.25
90
-1.00
120
-0.25
150
1.25
180
2.00
104

The dz2polar plot is present for every value of , i.e., it
is independent of . Thus the dz2 orbital consists of
two lobes of the same sign lying along the z-axis, plus a
smaller doughnut-shaped lobe of opposite sign
which lies in the xy-plane.
The other four d-orbitals have four equal lobes, which
point towards the corner of a square with the
nucleus lying at the junction of the lobes.
Three of these orbitals have their lobes lying between
the axes (dxy, dxz, and dyz). The fourth orbital (dx2 -y2)has
its lobes lying along the xy-axes.
105

The dz2orbital looks different from the other four dorbitals. However, the five d-orbitals are essentially
equivalent.
106
Complete Wavefunctions
Complete wavefunctions are obtained by taking the product
of the radial and angular functions:
2 expresses the probability that the electron will be within

a particular very small volume element of the atom.
Whilst c an be positive or negative, 2 will always be
positive.
107
Electron Probability Density

An electron probability density diagram is sometimes used
to depict the probability of finding an electron at a certain
volume element.
The value of 2 is
represented by the
density of the
dots.
The greater the
density of dots, the
higher the probability
of finding the
electron at that small
volume.
108
Boundary Surfaces
How far away can e- be? Essentially
there is no limit: r = 0
So there is no boundary unless we
place an artificial limit upon the
wavefunction limit upon it.
The most common is to define the
size of an orbital as that of a contour,
inside which the electron has a
definite probability of being found.
The contour which defines the 90%
chance of finding the electron form
the boundary surface.
109
Energy Levels of One Electron Atoms

and Ions.
The solution of the Schrdinger equation reveals that the
energy of the wavefunction can have only certain values, given
by:
So the only quantum number that the energy depends on is n

(i.e., it is independent of l and m).
Thus, for the H atom (or the He+ or Li2+ ions) the 2s and 2p
energies are equal. Similarly, the 3s, 3p, and 3d orbitals have
equal energy.
Orbitals that have the same value of n are said to belong to
the same shell of the atom.
110

and Ions.
All the energy levels have negative values.

The zero of energy occurs when the electron and nucleus are
infinitely widely separated and are stationary.
The state of the lowest energy for the H atom (Z=1) occurs
when n=1. This is known as the ground state of the atom.
For hydrogen:
111

and Ions.
The first excited state occurs at n=2.This state has an energy
of:
The n=3 lies at: -1.51 eV.

The n=4 lies at: -0.85
eV.
Given this data, an
energy level diagram
can be constructed.
112

and Ions.
In a transition an electron jumps from an energy level (En2) to

a lower level (En1). In this transition the energy change is:
The sudden change of the electron as it changes its spatial

distribution from one orbital to another is said to jolt the
electromagnetic field into oscillation.
This oscillation results in the emission of a photon.
113

and Ions.
Not all transitions are allowed!
In any transition the angular momentum must be conserved.
A photon has one unit of angular momentum.
Thus the angular momentum of the electron must change by
one unit to compensate for the angular momentum carried
away by the photon.
Consider the transitions possible from the n=3 to the n=1 levels.
114
Selection Rules.
The selection rules for
spectroscopic transitions
for the hydrogen (1
electron) atoms are:
l = 1 and m = 0, 1
There are no restrictions
on
n.
115
Wavefunctions and Orbital Energies of

One Electron Ions.
The important difference is the charge on the nucleus (i.e.,
Z=2, for He+ and Z=3 for Li2+.)
Consider the wavefunction for the 1s orbital:
The radial distribution function of the 1s

orbital of for H, He+, and Li2+ is
The effect of the extra positive charge is
to draw the electron towards the nucleus.
The size of the orbital is contracted due t o
increased nuclear charge.
116
Wavefunctions and Orbital Energies of

One Electron Ions.
The electron is more strongly bound to the nucleus.
The higher nuclear charge lowers the orbital energy through
increasing nucleus-electron attraction.
Example: An electron in the 1s orbital of He+ has a lower
energy (more stable) than the equivalent electron in H.
For He+ :
For Li2+ :
n=2 lies at: -13.6 eV.
n=1 lies at: -122.4 eV.
n=3 lies at: -6.04
eV. n=4 lies at: -3.4
eV.

117
Electron Spin.
The three quantum numbers that we have looked at (n, l,
and m) describe the following properties of an atomic
orbital.
a)
Energy (n,l)
b)
Size (n,l)
c)
Shape (l,m)
d)
Orientation (m)
However, an additional quantum number is required in order to

describe a property of the electron itself - spin.
The electron spin is not a property of the orbital.
118
Electron Spin.
When a beam of hydrogen atoms passes through a non-uniform
magnetic field it splits into two beams that bend away from
each other.
This is due to the fact that the electron generates a tiny
magnetic field as though it were a spinning charge.
119
Electron Spin.
The single electron in each H
atom can spin in one of two
opposite directions, each of
which generates a magnetic
field.
The opposing directions of

these fields causes half
of the electrons to be
attracted into the region
of the external magnetic
field and half to be
repelled.
120
Electron Spin.
The quantum number, ms, was introduced to indicate the
direction of electron spin about its own axis.
The electron spin can have one of two possible values:
As a consequence, each electron in an atom is described

completely by a set of four quantum numbers.
For example: in the He atom:
121
Pauli Exclusion Principle.

No two electrons in an atom can
have the same four quantum
numbers.
This principle is more of a
consequence of the more general
Pauli principle, which states...
The total wavefunction must be

antisymmetric under the interchange of
any pair of identical fermions and
symmetric under the interchange of any
pair of identical bosons.
122
Energy Levels of Many-Electron Atoms

Because ms can have only two value (+1/2
or -1/2) the major consequence is that
each atomic orbital can hold a maximum
of two electrons - and they must have
opposite spin.
So what does this do to the forces acting
on each electron?
- Each electron will feel the nuclear attraction
(as in the one electron system).
- In addition there will be the electron-electron
repulsion.
123
Helium
In the case of He, the two electrons (with
opposite spin) occupy the 1s orbital.
- If a beam of He atoms is passed through a nonuniform magnetic field the beam is not split as
there is no net magnetic field on each atom.
However, the addition of an electron to the 1s

orbital, relative to He+, increases the energy
of this orbital.
- He+(1s) = -5248 kJ/mol
- He(1s) = -2372 kJ/mol
Thus, it takes less than half the energy to

remove an electron from He(1s2), than it does
to remove the electron from He+(1s1).
124
Helium
The electron-electron repulsion raises the
orbital energy (makes it less stable), which
makes it easier to remove an electron
from the orbital.
Each electron shields the other electron, to a
certain extent, from the full nuclear charge.
This shielding (also known as screening)
reduces the full nuclear charge to an effective
nuclear charge (Zeff).
Z is the nuclear charge the electron actually
eff
experiences.
125
Lithium
Li (Z=3) has a 1s22s1 electronic configuration.
The singly occupied 2s orbital of Li has an orbital energy
of -520 kJ/mol. However, in Li2+ if the 2s orbital is singly
occupied, the orbital energy is -2954 kJ/mol.
The energy difference arises
because the inner 1s2 electrons
spend the majority of their time
between the outer 2s1 electron
and the nucleus.
Thus the 1s2 electrons shield the
2s1 electron very effectively
and
this makes the outer
electron
much easier to remove.
126
Lithium
In a H atom, orbitals that have the same principal quantum number

(e.g., 2s and 2p) have the same energy.
Why is it that in many electron atoms the 2s more stable than the
2p?
The 2s electron is, on average,
slightly further away from the
nucleus than the 2p electron.
Hence we expect the 2s
electron to be easier to
remove. This implies the 2s
orbital is higher in energy.
There is a small portion of the

2s RDF that appears very
close to the nucleus. It
penetrates more through the
inner shell than the 2p RDF.
127
Lithium
This means that the 2s electron experiences less
shielding than the 2p electron.
Therefore the 2s electron experiences a larger Zeff and is
more stable than the 2p electron.
In general, for electrons of the same shell the
penetration of the orbital is smaller as the value of l
increases.
Penetration: s > p > d > f
Order of subshell energies: s < p < d < f
128
Potassium
As n increases the shell energies, and in particular the
sub-shell energies become closer together.
Therefore we get the situation where the 4s is slightly
lower in energy than the 3d sub-shell, and so the 4s
sub-shell is filled first.
For example, in the case of potassium (K) where
Z=19:
129
Potassium
This can be explained by considering the RDF of 4s and 3d
orbitals.
- Most of the electron density of the 3d orbital is closer to the
nucleus than the main concentration of the 4s orbital (Hence, in
a H atom the 3d is more stable than the 4s).
- The 3d orbitals are well shielded from the nucleus, however the
4s orbital is able to penetrate the inner shells because a small
proportion of its density lies closer to the nucleus.
130
Potassium
An electron in the 4s orbital experiences a greater
(Zeff) than an electron in the 3d orbital.
This makes the 4s orbital more stable than the 3d
orbital in K.
131

Quantum Mechanics

Hochgeladen von

Dokumentinformationen

Originalbeschreibung:

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Quantum Mechanics

Hochgeladen von

Copyright:

Verfügbare Formate

Physical Chemistry II

Bonding and Symmetry

Sir. Isaac Newton

Wilhelm Carl Werner Otto

How come infrared satellites

Blackbody Radiation - The

Blackbody Radiation - The problem...

E = energy of the radiation

This gives very good

is long, we can replace

Therefore, at long wavelengths:

Plancks theory for BBR!

The Photoelectric Effect

So... Why is this strange?

Double Slit Experiment

So... Why is this strange?

Problems: Wave Theory of Light.

Einsteins theory for PEE!

The number of electrons emitted in dim light is smaller than the

Einsteins theory for PEE!

Atomic Emission Spectra.

Atomic Emission Spectra.

The wavelengths of the lines are given by:

In the Lyman series: a=1, b=2,3,4,...

Atomic Emission Spectra.

The Bohr Theory (of Hydrogen).

The Bohr Theory (of Hydrogen).

The energy of an orbit is

The Bohr Theory (of Hydrogen).

The LES of hydrogen (Bohr).

The LES of hydrogen (Bohr).

The Maybe Not So Good Stuff.

An -particle (6.6 x 10-27 kg) moving at 1.5 x 107 ms-1 ?

The wavelength of an electron.

An electron of mass 9 x 10-31 kg

Now if particles do behave like

Waves exhibit a diffraction

The wavelength of an electron.

Heisenberg Uncertainty Principle.

Heisenberg Uncertainty Principle.

The more precisely we know the position of the particle,

Heisenberg Uncertainty Principle.

The diameter of the atom is of the order 10-10 m. Therefore, we have no

When this occurs the wavefunction is said to be

Foundations of Quantum Theory

The foundations are based on two postulates.

Consider a system of n particles which could be

Foundations of Quantum Theory

This contains all there is to know about the system, all

There are four further conditions to the normalisation

These conditions imply that there are

There are two ways we can obtain the value of the

This is known as an EIGENVALUE equation, where o is the

In order to obtain a quantum mechanical operator, one

(b) replacing each cartesian component of pk

Note: if the charges have the same sign, then the

The kinetic energy terms are

And recall i2=-1.

Particle in a One-Dimensional Box

Particle in a One-Dimensional Box

The Schrdinger Equation is:

Which, for our 1-D box, yields:

Particle in a One-Dimensional Box