Chapter 12
Elements of Physical Chemistry
Atkin & dePaula
The Emergence of Quantum Theory
Classical mechanics (Isaac Newton, late
19th century) for law of motion of macroscopic
objects
Early 20th century, it was found that
classical mechanics does not correctly
describe behavior of sub-atomic particles.
Behavior of such particles is described by
quantum mechanics
Quantum mechanics is the latest theory for
description of matter
Assumptions of classical mechanics
A particle travels in a trajectory, a path with
a precise position and momentum at each
instant.
Any type of motion can be excited to a state
of arbitrary energy.
Waves and particles are distinct concepts.
Classical mechanics fails
When applied to individual atoms and
subatomic particles
when the transfer of energy is very small
Examples of failures of classical mechanics
Black-body radiation
Heat capacities
Photoelectric effect
Compton effect
In classical physics light is described as
electromagnetic radiation travelling at a speed of
light c=3 x108 m s-1
Electromagnetic field has
two components,
an electric field (acts on
charged particles)
a magnetic field (acts on
moving charged particles)
Electromagnetic field is
characterized by
wavelength() and
frequency() : = c
The electromagnetic spectrum
Photoelectric effect
Under the right circumstances light can be used to
push electrons, freeing them from the surface of a
solid. This process is called the photoelectric effect
(or photoelectric emission or photoemission)
The ejected electrons are called photoelectrons
First observed in 1887 by Heinrich Hertz
Features of Photoelectric Effect (summary)
No electrons are ejected, unless the frequency
exceeds a threshold value
The kinetic energy of the ejected electrons varies
linearly with the frequency of the incident radiation
Even at low light intensities, electrons are ejected
immediately if the frequency is above the threshold
value
: the
1
E K m e v 2 h eV s
2
energy required to remove an electron from
the metal to infinity is the work function of the metal;
Vs: stopping potential
When h
photoejection cannot
occur as photon supplies
insufficient energy to expel
electron
Kinetic energy of an
ejected electron should
increase linearly with the
frequency
Photoelectric effect
we can think radiation as a stream of particles, each
having an energy h
Particles of electromagnetic radiation are called photons
When a photon collides with an electron, it gives up all
its energy, so electrons are expected to appear as soon
as the collisions begin
Photoelectric effect confirmed that radiation can
be interpreted as a stream of particles
The diffraction of electrons
Diffraction is the interference between waves caused
by an object on their path
Results in series of bright and dark fringes
Diffraction is a typical characteristic of wave
Davisson-Germer
experiment showed the
diffraction of electrons by a
nickel crystal
This experiment shows
that wave character is
expected for the particles
Wave-Particle duality
Particles have wave-like properties and waves have
particle-like properties when examined on an atomic
scale (i.e. the concepts of particle and wave melt
together);
particle taking on the characteristic of waves and
waves the characteristics of particles
This joint wave-particle character of matter and radiation
Is called wave-particle duality
How to describe wave-particle duality?
de Broglie relation
h
p
Linear momentum of the travelling particle
Wave length of that particle
Wavelength of a
particle should decrease
as its speed increases
For a given speed,
heavy particles should
have shorter
wavelengths than lighter
particles
Classical physics:
an oscillator can have any energy
Quantization of energy
energy
of
each
electromagnetic oscillator is
limited to discrete values
and cannot be varied
arbitrarily.
permitted energies of an
electromagnetic oscillator
E = nh n = 0, 1, 2,
Planck constant
h = 6.626 x 10-34J s
Atomic and molecular spectra
atomic emission
molecular absorption
Atomic and molecular spectra
Radiation is emitted and
absorbed at a series of
discrete frequencies
This supports the
discrete values of
energy of atoms and
molecules
Then energy can be
discarded or accepted
only in packets
Classical mechanics Quantum mechanics
Governed by
Newtons 2nd law
Governed by
Schrodinger equation
Deterministic
Probabilistic
Continuous energy
Discrete energy
Wave & particle are
different concepts
Wave-particle duality
Description of a quantum mechanical
system
Description of a quantum mechanical system
Classical mechanics: well defined trajectory with
precise position and momentum
Quantum mechanics: a particle cannot have a precise
trajectory, there is only a probability
A particle is spread through space like a wave
There are regions where the particle is more likely to
be found than others
To describe this distribution the concept of wavefunction
is introduced, in place of trajectory
Dynamics of microscopic systems
The wave function that
determines the particles
probability distribution is
a kind of blurred version
of trajectory
A wave function is the
modern term for de
Broglies matter wave
Wave function: it is a mathematical function that
contains all the dynamical information about the state
of a system
The Schrdinger equation
Schrdinger Equation for a single particle of mass
m and energy E (in one dimension)
2
2m dx
2
V : Potential energy
h
=1.054 x 10-34 J .S
2
2
d
H E ; H
V
2
2m dx
We can justify the form of Schrdinger equation
If V = 0
E
2
2m dx
2
( 2mE )
and a solution is S in k x where k
Comparing Sink x With the standard form of a
harmonic wave of length , which is
2x
Sin
we get
1
2
1 2 m v
p
mv
Energy E =
2
2m
2m
2
k
But E =
2m
2 h
h
p k
2
This is de Broglies relation.
So Schrdinger equation has led to an
experimentally verified conclusion
Solution of Schrodinger Equation
Infinite number of solutions are allowed mathematically
Solutions obeying certain constraints called
boundary conditions are only acceptable
Each solution correspond to a characteristic value of
E. Implies Only certain values of Energy are acceptable.
Energy is quantized
The Born interpretation
(a)Wavefunction
No direct physical interpretation
(b) Its square (its square modulus
if it is complex)
probability of finding a particle
(c) Probability of finding a
particle in a small region of
space
of
volume
V
is
proportional to 2 V
2 is probability density
Wherever 2 is large, there is high probability of
finding particle
The Born interpretation
Acceptable wavefunctions
Must be:
(a) single valued
(b) finite
(c) continuous
(d) continuous
slope
The uncertainty Principle
It is impossible to specify simultaneously, with arbitrary
precision, both the momentum and the position of a
1
particle.
p x x Where, p x and x
2
Are uncertainty in the linear position and momentum, respectively
If we know the position of
a particle exactly, we can
say nothing about its
momentum and vice
versa.
Particle with a well defined position
A sharply localized wavefunction
can be obtained by adding
wavefunctions
of
many
wavelengths, therefore, by de
Broglie relation, of many different
linear momenta
As the number of function
increases wavefunction becomes
sharper
an infinitely narrow spike if an
infinite no. of components are used
discarding all information about
momentum perfect localization
Applications of quantum mechanics
Translation: a particle in a box
A particle in a one-dimensional region
Impenetrable Walls at either end
Its potential energy is constant between x=0 and x=L
It rises abruptly to infinity as the Particle touches wall
Boundary conditions
The wave function must be zero where V is
infinite, at x<0 and x>L
The continuity of the wavefunction then requires
it to vanish just inside the well at x=0 and x=L
The boundary conditions for this system are the
requirement that each acceptable wavefunction
must fit inside the box exactly
2
2L
2 L , L , L ,......or
, with n=1,2,3
3
n
Each wavefunction is a sine wave with one of these
2
2L
wavelengths 2 L , L , L ,......or
3
n
2x
sin
sine wave has the form
permitted wavefunctions are
n x
n N sin
L
N is the normalization constant
It is chosen such that the total probability of
finding the particle inside the box is 1
The total probability of finding the particle between
x =0 and x =L is 1
(the particle is certainly in the range somewhere)
L
dx 1
Substituting
n x
N sin
dx 1
L
0
L
1
N L 1
2
2
and hence
2
N
L
1
2
Permitted Energies of the particle
p2
The particle has only kinetic energy
2m
The potential energy is zero everywhere inside
the box
h nh
n 1, 2 ,....
de Broglie relation shows p
2L
Permitted energies of the particle
n2h2
En
n 1, 2 ,..
2
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n is the quantum number
The allowed energy levels & (sine wave) functions.
Number of nodes
n-1
The energy difference between adjacent levels is
2
h
E E n 1 E n ( 2 n 1)
2
8m L
1. Greater the size of the system
Less important are the effects
of quantization
2.Greater the mass of the particle
Less important are the effects
of quantization
Zero Point Energy
Quantum number n cannot be zero (for this system)
The lowest energy that the particle possess is not zero
h2
2
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This lowest irremovable energy is called the
zero point energy
The existence of a zero-point energy is consistent
with the uncertainty principle
