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
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
in packets
Conclusion:
Internal modes of atoms and
molecules can possess only
certain energies
These modes are quantized

A typical atomic emission spectrum

Shape is due to the

combination of
electronic and vibrational
Transitions of a molecule

A typical molecular absorption spectrum

Photoelectric effect
we can think radiation as a stream of particles, each
having an energy h

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

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

1
2
me v = h
2

is the work function of the metal

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

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 the interference between waves caused by
an object on their path
Series of bright and dark fringes

Diffraction is a typical characteristic of wave

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
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

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

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

Dynamics of microscopic systems

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
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
determines its probability
distribution is a kind of
blurred version of trajectory

The Schrdinger equation

Schrdinger Equation
2

h d

+ V ( x) = E
2
2m dx

or

H = E

Hamiltonian
Schrdinger equation for a single particle of mass
M and energy E (In one dimension)
V
Potential energy

h
=1.054 x 10-34 J .S
2

We can justify the form of Schrdinger equation

(in case of a freely moving particle) V = 0 everywhere
2

h d

= E --------------(1)
2
1
2m dx
(2mE ) 2
A solution is = Sinkx where k =

=
Sinkx
[ can be verified by putting
in (1)]
Comparing Sinkx With the standard form of a
harmonic wave of length , which is

Sin
2
we get =
k

2x

1 2 (mv )
p
mv =
=
Energy E =
2
2m
2m
2

k h
But E =
2m
2

h
h

=
p = kh =
2

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 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)
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

1
px h
2

p Uncertainty in the linear momentum

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

px

py

pz

x
y
z
px
py
pz

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
2L
= 2 L, L, L,......or =
, with n=1,2,3
n
3

Each wavefunction is a sine wave with one of these

2
2L
wavelengths = 2 L, L, L,......or =
3
n
sine wave has the form

2x
sin

permitted wavefunctions are

nx
n = N sin
L

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)
L

dx = 1

Substituting

nx
N sin
dx = 1
L
0
2

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

de Broglie relation shows p = = 2 L n = 1,2,....
Permitted energies of the particle
n2h2
En =
2
8mL

n = 1,2,..

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

h2
8mL2

This lowest irremovable energy is called the

zero point energy

The energy difference between adjacent levels is

h2
E = En +1 En = (2n + 1)
2
8mL
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

Vibration: the harmonic oscillator

Hookes Law:
Restoring force =

k
x

kx

is the force constant and

is the displacement

1 2
Potential energy (V ) = kx
2

After solving Schrdinger equation

The only allowed energies are
1
E = ( + )h
2
= 0,1,2,......1
1 k 2
=

2 m

is the vibrational quantum

number

is the frequency (in cycles

per second or hertz, Hz)

(a)The wavefunctions (b) the probability densities

of the first three states of harmonic oscillator