CHEMISTRY I (CHEM C141)

K. Sumithra

Lecture 3: 9/8/2010

SUMMARY OF THE LAST LECTURE

Black Body Radiation - features

Plancks Distributions:
Concept of Quantization
Photoelectric Effect: Ek = h = h( 0)
Particle nature of light

Line Spectra: E = E2 E1 = h
Convincing evidence for Quantization
Bohr Atom Model

Atomic and Molecular Spectra

A region of spectrum of radiation

emitted by exited iron atoms

Spectrum due to sulphur dioxide

molecules

The energy of the atoms or molecules is confined to discrete

values, so energy can be discarded only in packets.

Bohr model of hydrogen-like atom

To account for the line spectrum, Bohr proposed

stable orbits (or energy levels), for the electron,
given by the quantization condition for angular
momentum

mvr = nh/2 = n, n = 1,2,3,.

Bohr Model
1. Specific orbits, discrete quantized energies.
2. The electrons do not continuously lose energy, but gain
or lose by jumping from one orbit to another
3. quantization of angular momentum
L = mvr = nh/2 = n, n = 1,2,3,.
Success

Could explain Rydbergs formula

Theoretical background for Line Spectra

Bohr model Inadequacies

Primitive Model
Semi-classical
The spectra of larger atoms.
The relative intensities of spectral lines.
The existence of fine and hyperfine structure
in spectral lines.
The Zeeman effect - changes in spectral lines
due to external magnetic fields.

Waves and Particles

Main experiment showing light as particles
are the
Photoelectric effect
Black body radiation

Two properties of waves are:

Interference
Diffraction
If electron is acting as a wave,
We should see diffraction and interference
of matter waves

Wave-Particle Duality
Wave-Particle duality shows:

Light can act like a particle.

Particles can act as waves

Double-slit Experiment

Interference: Superposition of two or

more waves to generate new patterns
Constructive; destructive

Youngs double-slit experiment

can be done with electrons

Electron behaving as a wave!

The wavefronts resulting
from two slits.

Interference
constructive

destructive
combined
waveform
wave 1
wave 2

Two waves in
phase

Two waves
180 out of
phase

Electron Diffraction
Firing electron at an object and observing the
scattering (analogous: X-ray and neutron
diffraction): Davisson and Germer 1925

investigation of the angular distribution of electrons

scattered from nickel. :
electron beam was scattered by the surface atoms at the exact angles
predicted for the diffraction of waves, with a typical wavelength

Braggs law
n=2d sin()

A pattern of sharp reflected

beams from the crystal

- wavelength of the electron wave

Duality

Girl friend or her Granny?

wave-particle duality
The ability for something to behave as a
wave and a particle at the same time is
known as wave-particle duality.

Duality is a paradox
It combines two contradictory features or qualities
That does not mean that it is false!
It is a fundamental property of the universe.

Matter-Wave Duality
Orthodox Quantum physicist :
Duality is a phenomenon that can be viewed in
one way or in another, but not both
simultaneously.
Second-order consequence of various limitations
of the observer
Waveparticle duality is deeply embedded into
the foundations of quantum mechanics

It is difficult to draw a line separating wave

particle duality from the rest of quantum
mechanics.
Applications of Duality
1. In electron microscopy
where the small wavelengths associated with the
electron can be used to view objects much smaller than
what is visible using visible light.
2.

Neutron Diffraction
uses neutrons with a wavelength of about
1 , the typical spacing of atoms in a solid, to
determine the structure of solids.

Evidence for wave-particle duality

Evidence for particle-nature of light
Photoelectric effect
Compton effect
Evidence for wave-nature of matter, light
Electron diffraction
Interference of matter-waves
There are therefore now two theories of
light, both indispensable, and without any
logical connection.
Einstein, 1924

Light comes in discrete units (photons) with

particle properties (energy and momentum)
that are related to the
wave-like properties of frequency and wavelength.
MATTER WAVES
Prince Louis de Broglie 1923
Postulate :

Ordinary matter can have wave-like properties,

with the wavelength related to momentum p.

Matter waves
de Broglie:

p = h/
A particle moving with linear momentum p,
has an associated matter-wave of wave
length: = h/p

Wave-Particle Duality

 = h/p

 Calculate the wavelength of an electron in a

10-MeV particle accelerator. (1 MeV = 106 eV)
Solution:

We need to find the momentum, p, from the

energy, E.
The relationship between them is p = (2mE)
P = (2 x 9.11 x 10-31 kg x10 x106 x 1.602 x 10-19 kg
m2 s-2)
= 1.7 x 10-21 kg m s-1
= h/p = (6.626 x 10-34 J s)/(1.7 x 10-21 kg m s-1)
= 3.9 x 10-13 m = 0.39 pm

Largest object for which quantum-mechanical wavelike properties have been directly observed in
diffraction.
C60 fullerenes wave manifestation:
Large, massive object
(diameter is in nanometer range)

de Broglie wavelength is 2.5 pm i.e. about 400 times

smaller than diameter.
Journal: Nature 401: 680-682, 1999
University of Vienna, Austria.

Buckminsterfullerene
Bucky ball

Are there waves associated with macroscopic objects?

Wavelengths are immeasurably small

Some Typical de Broglie wavelengths

An electron accelerated through a potential

difference of 50 V
~ 1.73 x 10-10 meters.

A ball weighing 100 g, and moving with a speed

of 25 m/s
~ 2.65 x 10-34 meters.
A human being weighing 70 kg, and moving with a
speed of 25 m/s
~ 3.79 x 10-37 meters.

Duality ; Consequence

Uncertainty Principle
No physical phenomena can be described by only
classic point particle or wave Neither the wave or
particle description is fully and exclusively accurate

Uncertainty

A property of Conjugate variables :

share an uncertainty relation
Time and Frequency
Position and Momentum

Heisenbergs Uncertainty Principle

It is impossible to specify simultaneously,
with arbitrary precision, (a given Cartesian
component of) the momentum and position
of a particle.

px x /2
mv.x h/4
x- uncertainty in position

=h/2

p- uncertainty in momentum

Complementary variables, increase in the precision of

one possible only at the cost of a loss of precision in the
other.

Uncertainty Principle

Definite wavelength Definite momentum but since

wave is spread out everywhere, no information about
position.

Hard to understand duality, matter waves, uncertainty?