At resonance

ωR is the Rabi frequency.

System is coherently cycled between the ground and exited state by EM

Need to consider decay processes such as Spontaneous emission and collisional relation process
They would change the phase of the wavefunctions and damp the oscillation.

Exercise:- Consider 1-W laser system with 1 mm beam cross section interacting the a
2 level system. The transition dipole moment = 3.335 x 10-30 C m. What is the Rabi frequency?
Assuming there is no collision will there be any damping due to spontaneous emission?
(Natural lifetime of for electronic transitions are usually about 10 ns)
In case of a weak field the ground state is mostly populated and so a 0 ≈ 1, then

Upon integration

The probability to find the system in the excited state after a time t is then given by
But is it purely monochromatic light?

It is actually a narrow band of frequency with radiation density given by

Then the transition probability is given by

Absorption rate per molecule is then

For weak field case N0 ≈ N , and

Absorption cross section is then
If a flux F is incident to the left of a small element of thickness dx , with 1 sq.m. cross section
then the change in flux is given by

Upon integration,
Lineshape functions

Consider the absorption spectra of CO2

Homogeneous and inhomogenous lineshape functions

Pressure broadening is homogenous

Molecule in a inhomogenous solvent gives inhomogenous broading and so is doppler

broadening
Nature lifetime broadening

Consider a two level system with intrinsic spontaneous decay lifetime τsp

Wavefunction of the two level system is given by

Now let a pulse of EM wave excite the system into this superposition state then the
dipole moment in this state is given by

Dipole moment hence oscillates at the Bohr frequency as

Now due to spontaneous decay rate of γ = 1/ τsp , a1 would decrease at the rate of γ/2

Hence the amplitude of the oscillating dipole would decrease like

Bohr Frequency

Band of frequency
Oscillating dipole emits radiation of Bohr frequency but the damped oscillation of dipole
would yield a band of frequency

Lineshape, which is a Lorentzian

Need to normalize it
Lorenztian lineshape function with finite width

???
Effects of Spontaneous emission and Collisions

With
 Rotational spectroscopy

Relationship between the angular momentum and the angular frequency

Where I is the moment of inertia

Moment of Inertia

Product of inertia