Line-Broadening Mechanisms

& Nonradiative Decays

Homogeneous and Inhomogeneous

Broadening
If a mechanism broadens the lineshape the
same way for each atom, it is homogeneous.
If the mechanism distributes the resonance
frequencies over a spectral range , it is
inhomogeneous.
Now we are going to examine various physical
mechanisms.

Measurement of a Lineshape
The total lineshape for a system can be easily measured through
absorption spectroscopy.

Spectrometer

abs.spectrum

intensity

intensity

White light

m
e
d
i
u
m

wavelength

wavelength

Collision Broadening
Collision broadening results from atomic/molecular collisions in a gas, or from
interaction with lattice phonons in a solid.

Collision broadening is homogeneous.

Collisions cause random phase jumps in the wavefunctions.
Alternatively, we can also think that the incoming electric field goes through
phase jumps.

The new field is no longer monochromatic.

Collision Broadening (contd)

For a monochromatic wave, the absorption (and S.E.) rate was given by:

Since the field is now not monochromatic, we have a distribution of energy density
over frequencies. The elemental transition rate for an infinitesimal range is:

The overall rate is found by integration:

Collision Lineshape
We now introduce the collision lineshape:

The lineshape should be

normalized:

Using the property of the delta function, we get:

Collision Lineshape
If the average time between collisions is c, then the lineshape is given
by a Lorentzian:

The bandwidth is:

Collision Broadening: Example

Lets estimate collisional broadening for a He-Ne laser. In a gas at pressure p,
and atomic mass M, collision time is given by:

For Ne at 0.5 atm, we find:

The frequency of the emission is (632 nm):

Therefore the light is still highly monochromatic.

Natural Broadening
Natural (or intrinsic) broadening originates from spontaneous emission and
results from quantum nature of energy levels. The uncertainity principle sets
a limit between lifetime and tansition energy.

Natural Broadening is homogeneous. It is also given by a

Lorentzian, but with a new bandwidth and collision time:

We previously estimated lifetime for a visible transition as 10 ns. As

a result, for that transition we have:

Broadening Due to Impurities

If there is an impurity (inhomogeneity) in a symmetric medium, like
glass, nearby atoms will experience a local electric field. This field will
affect the electron energy levels, known as Stark shift.
The result is an inhomogeneous broadening. It will shift the
resonance frequencies. The new distribution of resonant frequencies is
given by a function g*.
Inhomogeneous distribution functions are typically Gaussian.

The bandwidth *0 depends on the impurities.

Inmomogeneous broadening due to impurities

is particularly strong in glasses.
Nd:Glass laser: The main laser transition is at 1.05 m. The bandwidth
due to impurities in glass becomes:

This broad bandwidth supports short pulse durations.

The Doppler Effect

The doppler effect tells us that the frequency of waves depends on the
motion of source and observer.

The doppler effect also happens for electromagnetic waves.

Doppler Broadening
Assume that an atom/molecule is moving in z-direction with velocity vz.
If an electromagnetic wave of frequency is incident, the frequency seen by
the atom is:

When the atom is moving away from the light source, the radiation
frequency is red-shifted. When it is moving towards the source, frequency
is blue-shifted.
Absorption happens when the doppler-shifted frequency coincides with the
transition resonance frequency:
OR:
We can interpret this as a shift of resonance frequency:

Hence, the Doppler broadening

is inhomogeneous.

Doppler Lineshape
Velocity distribution in a gas is given by Maxwell distribution:

/
The velocity distribution is the same as resonant frequency distribution:

We again obtain a Gaussian lineshape with

a bandwidth:

Doppler Linewidth of a He-Ne Laser

At 300 K, the doppler linewidth for Ne is:

You will calculate average velocities and this bandwidth in

a HW problem.

Combination of Broadening Mechanisms

Homogeneous broadenings always give a Lorentzian.
Inhomogeneous broadenings always give a Gaussian.
Overall lineshape of different effects is given by a convolution:

If two homogeneous mechanisms overlap, the total lineshape is another Lorentzian

with a bandwidth:
If two inhomogeneous mechanisms overlap, the total lineshape is another Gaussian
with a bandwidth:

The proof is a HW problem.

Non-Radiative Decay
An excited state can also decay via
non-radiative processes.
The detailed description is complicated.
We will only do a qualitative discussion.
We will also consider radiative and nonradiative processes combined.

Collisional Deactivation
For a gas or liquid, the energy is transferred to the colliding species as
excitation and/or kinetic energy.
In solids, the energy is transferred to the lattice phonons or vibrational
modes.
The deactivation can be represented as:

The process is particularly effective when mass of B is small. This is

used in CO2 laser, where He atoms take the surplus energy.

Collisional Activation
The reverse process can also take place i.e. species B can e excited by
taking up the energy of A:

The change of population due to both processes is given by:

In thermodynamic equilibrium:

However, in case of strong pumping, the term on the LHS is much

stronger.

Collisional Decay Rate

In case of strong pumping, we can neglect collisional activation.
Then we can write the rate equation as:

Or, by definign a nonradiative decay rate and lifetime:

Collisions may also excite/deactivate the

colliding species.
During a collision, apart from kinetic energy, internal energies may also shift.
This process is particularly important for gas lasers like He-Ne.

Combination of Radiative and nonRadiative Processes

If both radiative and non-radiative processes take place, we can write:

Or, by defining an overall decay time:

Which has a solution:

Spontaneous Emission Lifetime

Spontaneous emission results only from radiative processes. Hence the
emission power in a certain volume V is:

As a result, spontaneous emission decays with overall lifetime.

To find the radiative lifetime, we define fluorescence quantum yield
as (number of emitted photons)/(number of excited atoms):

We can measure the yield, and then determine radiative lifetime.

Saturation
Now we will consider emission and
absorption in presence of strong EM wave.
In this case, the energy level populations
differ strongly from equilibrium.
The consequent phenomenon is called
sarutation.

Saturation of Absorption: Homogeneous Line

Rearranging:

Steady state solution

At steady state:

OR

Where, using :
We get the saturation intensity:

When the intensity reaches the saturation, the level population

difference become N = Nt / 2. Then the emission processes balances
absorption. The absorption is hence saturated.

Change of a homogeneous line with saturation

Remember the absorption coefficient:

For homogeneous lineshape:

And defining:

Unsaturated absorption
coefficient

Absorption coefficient reduces with the

same lineshape.

Change of a homogeneous line with

saturation

Saturation of Gain: Homogeneous Line

As before, levels 3 and 1 decay rapidly, hence:

Where Rp is the pumping rate from g to 3.

At steady state:

Note that this is

twice the
saturation
intensity for
absorption.

Change of a homogeneous line with saturation

Now we will consider the change of gain
profile, rather than absorption.

As previous:
Unsaturated gain
coefficient

Gain coefficient reduces with the same

lineshape.

Inhomogneously Broadened Line

The saturating beam only interacts with atoms with resonance frequency in
the neighbourhood of light frequency.

Saturating beam burns a hole in the gain profile.