Chem 242

Dr.Salwa M. Al-Rashed
Associate Professor of Physical
Chemistry

2013-1434
 Quantum mechanics
Quantum mechanics began in 1900 when the study of light
emitted by heating solids was studied, so we begin by
discussing the nature of light.
In 1801Thomas Young gave convincing experimental
evidence for the wave nature of light by showing that light
exhibited diffraction and interference when passed through
two adjacent pinholes.
In 1860 Maxwell developed Maxwell’s equations
predicted that an accelerated electric charge would
radiated energy in the form of electromagnetic waves.
light is a type of energy and has wave properties
Electromagnetic (EM) radiation travels through space as electric
energy and magnetic energy.
Wavelength  and frequency  are related by:
 x  = c = 3.00 x 108 m/s
Frequency (or wavelength) determines the type of radiation All
electromagnetic waves travel at speed c= 3.00× 1010 cm/sec in
vacuum.
As a wave, we can describe the energy by its wavelength, which is
the distance from the crest of one wave to the crest of the next wave.
The wavelength of electromagnetic radiation can range from miles
(radio waves) to inches (microwaves in a microwave oven) to
millionths of an inch (the light we see) to billionths of an inch (x-
rays).

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The wavelength of light is more commonly stated in
nanometers (nm). One nanometer is one billionth of a
meter.
Visible light has wavelengths of roughly 400 nm to
roughly 700 nm. This range of wavelengths is called
the visible spectrum.

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The Wave Nature of Light

c    E  h 
The speed of light is constant
radio gamma-ray

visible
microwave infrared UV X-ray

106 105

wavelength (nm)
Low High
Energy
 (nm) Energy
 The speed of EM waves
• Observe what happens when a radio wave and a
visible wave move through space (at same speed of c)

Visual 6 Hz

Radio 3 Hz

• The longer the wavelength, the smaller the frequency

has to be to keep c constant
 The speed of EM waves
Q1 - Which of the following has the higher frequency
1. visible light or UV (choose one)
2. X-rays or radio waves (choose one)

Q2- Which of the following pairs has the longer

wavelength:
1. Infrared or Ultraviolet (choose one)
2. Gamma rays or Radio waves (choose one)
 Energy
Energy and
and Matter
Matter

Size of Matter Particle Property Wave Property

Large – macroscopic Mainly Unobservable

Intermediate – electron Some Some

Small – photon Few Mainly

For matter E = m c2 For waves E = h 

Exercises:
1.Photons have a wavelength of 500 nm. (The symbol nm is
defined as a nanometer = 1010 m) What is the energy of this
photon, and what is the type of the electromagnetic wave in
this case?

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Black body radiation
- A black body is a theoretical object that absorbs 100% of the
radiation that hits it. Therefore it reflects no radiation and
appears perfectly black.
- Roughly we can say that the stars radiate like blackbody
radiators. This is important because it means that we can use the
theory for blackbody radiators to infer things about stars.
- At a particular temperature the black body would emit the
maximum amount of energy possible for that temperature.
- Blackbody radiation does not depend on the type of object
emitting it. Entire spectrum of blackbody radiation depends on
only one parameter, the temperature, T.

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 Definition of a black body
A black body is an ideal body
which allows the whole of the
incident radiation to pass into itself
(without reflecting the energy) and
absorbs within itself this whole
incident radiation (without passing
on the energy). This propety is
valid for radiation corresponding to
all wavelengths and to all angels of
incidence. Therefore, the black
body is an ideal absorber of
incident radaition.

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The relationships between temperature, wavelength, and energy
emitted by an ideal thermal radiator (blackbody).

1. Based on everyday observations, the bodies at different temperatures emit

radiation (heat energy) of different wavelengths or colors. For example,
the wires in a heater begin to glow red when heated then the color of the
wire will changed by increasing the temperature.
2. Blackbody radiation is the theoretical maximum radiation expected for
temperature-related thermal self-radiation.
3. This radiation can have a peak energy distribution in the infrared, visible,
or ultraviolet region of the electromagnetic spectrum.
4. The hotter the emitter, the more energy emitted and the shorter the
wavelength. An object at room temperature has its peak radiation in the
infrared while the sun has its peak in the visible region.
5. The equations for calculating radiation based on temperature use the
Kelvin temperature scale. (Be sure to use the Kelvin scale for all
calculations).

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Color temperature

A light spectrum of
Blackbodies is often
characterized in terms
of its temperature
even if it’s not
exactly a blackbody.
 Thermal radiation spectral radiance

thermal radiation
 Thermal radiation: The radiation emitted by a body as a result of
temperature.
 Blackbody : A body that its surface absorbs and emit all the thermal
radiation incident on them.
 Spectral radiance: The spectral distribution of blackbody radiation.
RT ( )d : RT ( ) represents the emitted energy from a unit area per
unit time between and   d at absolute temperature T.
 The spectral radiance of blackbody radiation shows that:

1. The higher the temperature, the more the

emission and the shorter the average wavelength.

2. little power radiation at very low wavelength.

3. The power radiation increases rapidly as 
increases from very small value.
4. The power radiation is most intense at certain
wavelength max or max for particular
temperature.
5.   max and RT drops slowly, but continuously
as  increases, and RT(  ) 0.

6. max increases linearly with increasing

temperature.
7. The total radiation for all ν (radiance
RT= RT () d, increases less rapidly than
Now it is very important to find mathematical
equations shows the following relationships:
1.Inverse proportionality between max and T.
2.Direct proportionality between (RT d) or (E d)
with T.
3.The relation between (RT d) or (E d) and .

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Classical quantum mechanics of the black body
radiation:
The power radiated per unit surface area of the radiator is given by
the Stefan-Boltzmann law.
The Stefan-Boltzmann Law
* The amount of energy radiated is proportional to the temperature
of the object raised to the fourth power.
 The Stefan Boltzmann equation
F =  T4
F = flux of energy (W/m2)
T = temperature (K)
 = 5.67 x 10-8 W/m2K4 (Stefan-Boltzmann constant)
This law gives the total energy being emitted at all wavelengths by
the blackbody (which is the area under the Planck Law curve).
* Explains the growth in the height of the curve as the temperature
increases. Notice that this growth is very abrupt.
Classical quantum mechanics of the black body radiation:

Basic Laws of Radiation

1) All objects emit radiant energy.

2) Hotter objects emit more energy than colder objects (per unit
area). The amount of energy radiated is proportional to the
temperature of the object.

3) The hotter the object, the shorter the wavelength () of emitted
energy.

This is Wien’s Law

max  3000 m
T(K)
:Classical quantum mechanics of the black body radiation
b
max 
Wein Displacement Law T
- It tells us as we heat an object up, its color
changes from red to orange to white hot.
- You can use this to calculate the
temperature of stars.
The surface temperature of the Sun is 5778
K, this temperature corresponds to a peak
emission = 502 nm = about 5000 Å.
- b is a constant of proportionality, called
Wien's displacement constant and equals
2.897 768 × 10–3 m K = 2.897768 × 106
nm K.

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Classical quantum mechanics of the black body radiation:

 Stefan Boltzmann Law.

F =  T4

F = flux of energy (W/m2)

T = temperature (K)
 = 5.67 x 10-8 W/m2K4 (a constant)

 Wien’s Law

max  3000 m
T(K)
 peak vs Temperature
2.9 x 10-3 m
T peak = T(Kelvin)

3100K 2.9 x 10-3 m

(body temp) =9x10-6m
3100
infrared light

visible light
5800 K 0
2.9 x 10-3 m
(Sun’s surface) 58000 =0.5x10-6m
We can use these equations to calculate properties of
energy radiating from the Sun and the Earth.

6,000 K 300 K

T max region in F
spectrum
(K) (m) (W/m2)

Sun 6000 0.5 Visible 7 x 107

(green)

Earth 300 10 infrared 460

 Classical quantum mechanics of the black body radiation:
Wien's Law
To find a relation describe the relation
between the intensity of black body radiation
versus wavelengths for several temperatures
as given in the following figure. Many
theoretical physicists tried to derive expression
but they were all unsuccessful. One
expression that is derived according to the
laws of nineteenth century is Wien Law

C2 = h C/ k , C1= 8π h C

And it was found that for small wavelengths (high frequencies),

the previous equation fitted the experimental data but it deviate at
large wavelengths infrared waves.
 Classical quantum mechanics of the black body radiation:
The Rayleigh-Jeans Law
• The second atempt was by Rayleigh and Jeans how
use some assumptions to obtane the following
equation:

• This equation agrees with experimental

measurements for long wavelengths (low
frequencies) and failure at short wavelengths.
* It predicts an energy output that diverges towards
infinity as wavelengths grow smaller.
* The failure at short wavelengths has become known
as the ultraviolet catastrophe.

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Boltzmann Population Factors

N3 Ni is the number
E3
density of molecules
N i  exp   Ei / k BT  in state i (i.e., the
number of molecules
E2 N2 per cm3).
Energy

T is the temperature,
and kB is
Boltzmann’s
constant.
N1
E1

Population density
Quantum mechanics of the black body radiation
Planck’s Postulate and its implication

Planck’s postulate: Planck assumed that the radiation emitted

by the body was due to the oscillations of the electrons in
the constituent particles of the material body.
(i.e., simple harmonic oscillation can posses only total energy
  nh n = 1 ,2, 3---
Quantum mechanics of the black body radiation

Planck’s solution
EM energy cannot be radiated or absorbed in any
arbitrary amounts, but only in discrete “quantum”
amounts.
The energy of a “quantum” depends on frequency
as

Equantum = h 
h = 6.6 x 10-34 Js
“Planck’s constant”
 Planck’s quantum is small for “ordinary-sized”
objects but large for atoms etc
“ordinary” Hydrogen atom
pendulum   2x1014 Hz
= 1 Hz
e as
s am KE
t t he n’s
b ou
e ctro
a el
th e

Equant= h

=(6.6x10-34Js)x(2x1014Hz)
Equant= h =6.6x10 Jsx1Hz
-34

y =(6.6 x 2) x 10-34+14J
y tin
=6.6x10-34J ver
=1.3 x 10-19J
Classical vs Quantum world
At atomic & subatomic
In everyday life, scales,
quantum effects quantum effects
can be safely are dominant & must be
ignored considered

Laws of nature
This is because developed without
Planck’s constant is so consideration of
small quantum effects do not work
for atoms
The Planck Function

C2 = h C/ k , C1= 8π h C

• Blackbody radiation follows the Planck function at

all the wavelength range
 Black-Body Radiation Laws

Comparison of Rayleigh-Jeans law with Wien's law and Planck's law,

for a body of 8 mK temperature.
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Planck equation was applicable with practical results at short
wavelengths and long wavelengths. It is important to note that:
when λ is small, Planck equation can be reduced to Wien equation
by eliminating (-1) compared with the high value of the exponential
in the denominator in Planck equation,

Thus
While at large λ, Planck equation can be devolve into Rayleigh-
Jeans equation when compensated by the amount (1 +
C2/T)

Thus

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 Thanks for your attention

Any suggestions or questions are

.welcome

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