3 Crucially important Experiments

laid the foundation of QUANTUM THEORY

ATOMIC AND MOLECULAR SPECTRA
ENERGY TRANSFERRED, i.e., EMITTED OR ABSORBED,
WAS DONE ONLY IN DISCRETE QUANTITIES
PHOTOELECTRIC EFFECT PHOTOELECTRIC EFFECT
ELECTROMAGNETIC RADIATION (earlier considered to be
a wave) BEHAVED LIKE A STREAM OF PARTICLES.
ELECTRON DIFFRACTION.
ELECTRONS( which were believed to behave like particles
since their discovery) BEHAVED LIKE WAVE.
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 Then energy can be discarded or accepted only
in packets
Conclusion:
Internal modes of atoms and
molecules can possess only
certain energies
These modes are quantized
A typical atomic emission spectrum A typical atomic emission spectrum
A typical molecular absorption spectrum
Shape is due to the
combination of
electronic and vibrational
Transitions of a molecule
Photoelectric effect
we can think radiation as a stream of particles, each
having an energy h
Particles of electromagnetic radiation are called photons Particles of electromagnetic radiation are called photons
Photoelectric effect confirmed that radiation can be
interpreted as a stream of particles
No electrons are ejected, unless the frequency exceeds 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
= h v m
e
2
2
1

is the work function of the metal

When photoejection cannot occur as
photon supplies insufficient energy to expel electron
< h
Kinetic energy of an ejected electron should increase
linearly with the frequency
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
The diffraction of electrons
Diffraction is a typical characteristic of wave
Diffraction is the interference between waves caused by
an object on their path
Series of bright and dark fringes
Davisson-Germer experiment showed the diffraction of
electrons by a crystal
This experiment shows that
wave character is expected
for the particles
de Broglie relation
p
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 For a given speed, heavy particles should have
Shorter wavelengths than lighter particles
Wave-Particle duality
Particles have wave-like properties and waves have
particle-like properties
When examined on an atomic scale
the concepts of particle and wave melt together 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
A particle is spread through space like a wave
There are regions where the particle is more likely to be
found than others
Dynamics of microscopic systems
found than others
A wavefunction is the modern term for de Broglies matter
wave
According to classical mechanics a particle may have a
well defined trajectory with precise position and momentum
In quantum mechanics a particle cannot have a precise
trajectory, there is only a probability
The wavefunction that The wavefunction that
determines its probability
distribution is a kind of
blurred version of trajectory
The Schrdinger equation
Schrdinger Equation
E x V
dx
d
m
= +

) (
2
2
2 2
h
E H =

or
Schrdinger equation for a single particle of mass
M and energy E (In one dimension)
V Potential energy
h
2
h
=1.054 x 10
-34
J .S
We can justify the form of Schrdinger equation
(in case of a freely moving particle)
V = 0 everywhere
E
dx
d
m
=

2
2 2
2
h
Sinkx =
A solution is
--------------(1)
Comparing

x
Sin
2
With the standard form of a
harmonic wave of length , which is
Sinkx
k

2
=
we get
Energy E =
( )
m
p
m
mv
mv
2 2 2
1
2
2
2
= =
But E =
m
k
2
2 2
h

h h
k p = = =
2
h

h h
k p = = =
2
2
h
This is de Broglies relation.
So Schrdinger equation has led to an
experimentally verified conclusion
The Born interpretation
Probability of finding a particle in a small region
of space of volume V is proportional to
2
V

2
is probability density
Wherever is large, there is high probability Wherever
2
is large, there is high probability
of finding particle
Wherever
2
is small, there is small chance
of finding particle
Probabilistic interpretation
(a)Wavefunction
No direct physical interpretation
(b)Its square (its square modulus if
if it is complex) if it is complex)
probability of finding a particle
(c)The probability density
density of shading
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 uncertainty Principle
It is impossible to specify simultaneously, with
arbitrary precision, both the momentum and the
position of a particle
If we know the position of a particle exactly,
we can say nothing about its momentum.
Similarly if the particle momentum is exactly
known then its position will be uncertain
Particle is at a definite location
Its wavefunction nonzero there and zero
everywhere else
A sharply localized wavefunction by
adding wavefunctions of many wavelengths
therefore, by de Broglie relation, of many different
linear momenta
Number of function increases
wavefunction becomes sharper
Perfectly localized particle is
obtained
discarding all information about
momentum
Quantitative version of Uncertainty Principle
h
2
1
x p
p
Uncertainty in the linear momentum
x
Uncertainty in position
x
Uncertainty in position
Smaller the value of
, x
greater the uncertainty in
its momentum (the larger
value of
) p
and vice versa
Variable 1
Variable 2 x y z p
x
p
y
p
z

x
y
z
p
x

p
y

p
z


Observables that cannot be determined simultaneously with arbitrary precision
are marked with a grey rectangle; all others are unrestricted
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 zero 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
,......
3
2
, , 2
n
L
or L L L = =
with n=1,2,3
Each wavefunction is a sine wave with one of these
wavelengths

x 2
sin
2 2
2 , , ,......
3
L
L L L or
n
= =
permitted wavefunctions are
sine wave has the form
permitted wavefunctions are
L
x n
N
n

sin =
N is the normalization constant
The total probability of finding the particle between
x =0 and x =L is 1
(the particle is certainly in the range somewhere)
1
0
2
=

dx
L

Substituting Substituting
1 sin
0
2 2
=

dx
L
x n
N
L

1
2
1
2
= L N
and hence
2
1
2

=
L
N
Permitted Energies of the particle
The particle has only kinetic energy

m
p
2
2
The potential energy is zero everywhere inside
the box
de Broglie relation shows
nh h
p = =
,.... 2 , 1 = n
de Broglie relation shows
L
p
2
= =

,.... 2 , 1 = n
Permitted energies of the particle
2
2 2
8mL
h n
E
n
=
,.. 2 , 1 = n
n is the quantum number
The allowed energy levels & (sine wave) functions.
Number of nodes n-1
Zero Point Energy
Quantum number n cannot be zero (for this system)
The lowest energy that the particle possess is not zero
2
2
8mL
h
2
8mL
This lowest irremovable energy is called the
zero point energy
The energy difference between adjacent levels is
2
2
1
8
) 1 2 (
mL
h
n E E E
n n
+ = =
+
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
Motion in Two-dimensions
From separation of variables
Note: See Derivation 12.3
Degeneracy