Spontaneous Emission

If a molecule is situated in the upper level 2 (excited state), it will tend to lose its energy by
relaxation to the lower level 1 (ground state), giving out a photon of energy h21 during the
process. Einstein showed (using quantum electrodynamics) that for a single molecule the
probability of this ‘spontaneous’ emission of photon is described by

Where, 21 is the frequency of the emitted radiation (in Hz), 0 - the permittivity of the free
space, and μ12 is the transition dipole moment, (in C.m) [ ∫  , where 1 2 are
the wavefunctions for the ground and excited state, respectively ; μ is the electric dipole moment
operator for rotational, vibrational and electronic spectroscopy techniques, while μ is the
magnetic dipole moment operator for Electron Paramagnetic Resonance, Nuclear Magnetic
Resonance , Mossbauer spectroscopy and Nuclear Quadrupolar Resonance spectroscopy
techniques ; d is volume element with the integration is over all space; Moreover, the physical
interpretation of the transition dipole moment is that it is a measure of the magnitude of dipolar
migration of charge or magnetic moment that accompanies the corresponding transition]. The
spontaneous emission occurs when the molecule interacts with the electromagnetic field (EMR)
vacuum state, which is potentially the manifestation of zero-point energy oscillating
electromagnetic field. Interestingly, the zero-point oscillations of electromagnetic field can occur
even when there are no photons (h) present. These energy-less zero-point fluctuations of the
electromagnetic vacuum can cause ‘spontaneous’ transitions. Whereas spontaneous absorptions
in a zero-field fluctuations devoid of photons CAN NOT occur due to the conservation of energy
principle (i.e., without energy, we CAN NOT promote a molecule to its higher potential energy
state).

Each time atoms or molecules release spontaneous emission, they give out (lose) an amount 12
of energy. Thus, if there are N2 molecules in level 2 (excited state), the energy is emitted at the
rate
I21 (J. s 1) = N2h21A21

When we substitute the value of A21 on the above equation, then I21  4, i.e., the intensity of
the emitted radiation field depends on the fourth power of frequency. At regular intensities, the
relaxation of the sample system returning back to the lower level (ground state) is so rapid that
radiation field hardly causes any change in the population of atoms or molecules at the ground
state since molecules excited to the upper level (excited state) by the electromagnetic field are
substantially out of equilibrium. Spontaneous emission process (spontaneous relaxation
processes) restore the sample system back to equilibrium populations dictated by the Boltzmann
distribution law. These processes ‘spontaneous’ in the sense that they do not depend on the
radiation density. Thus the spontaneous emission becomes an important decay process as the
incident electromagnetic radiation frequency increases. At microwave frequencies, it is almost
irrelevant (A21 = 3  10 7 s 1 for  = 3 GHz), whereas in the ultraviolet region, it (radiative
‘spontaneous’ emission) is often the dominant relaxation mechanism ( for  = 230 nm, A21  3 

1
107 s 1) and thereby sets a limit to the lifetime of the molecule(s) in the upper level (excited
state).

Stimulated Absorption and Stimulated Emission

Stimulated (induced) emission and absorption processes are facilitated by a coupling (interaction)
between the oscillating transition dipole moment (μ12) and the oscillating electromagnetic field.
The stronger the field, the highly probably the transition is to occur. Einstein also showed that
the probability of the stimulated absorption for a molecule is:
P12 = (12)B12
where (12) is the radiation energy density (J.m 3) at a specific frequency (the energy in a region
of the oscillating field with the contributions arising from all components that have a frequency
in the range   Δ, divided by the volume of the field), and B12 is the Einstein stimulated
absorption coefficient

There is a concomitant equation for the stimulated emission process more akin to (similar to)
the probability for stimulated absorption equation. Since, the same transition moment governs
both upward and downward transitions, μ12 = μ21 , it follows that

B21 = B12  B

When a sample is irradiated with electromagnetic radiation of appropriate frequency, the

molecule which is occupying the upper level (excited state) is stimulated to move to the lower
level (ground state) with the same probability as that of the molecule in the lower level to the
upper level.

Net Absorption or Emission

So far, we have looked at the likelihood of a single molecule undergoing a transition between the
upper and lower levels. If we have a collection of molecules, another important factor we must
consider, viz., the number of molecules at a particular energy level, namely the populations of the
levels, N1 and N2, the populations of the lower and upper levels, respectively. Now, the
transitions that produce emission of radiation with intensity:

Iem. = Nh12[A+B.(12)]

While the upward transitions lead to net absorption, with intensity

Iabs. = Nh12B.(12)

The overall radiation effect is the difference between these two processes ; whether it corresponds
to net emission or absorption depends on whether N2 is greater than N1 or vice versa.

If N2 could be a significant fraction of N1, the energy difference must be quite small (in the range
of ~ 2 cm 1 to 0.000002 cm 1 at room temperature), in that case since probabilities of spontaneous

2
radiative emission as well as stimulated radiative emission processes are negligible, we can
ignore the contribution(s) made by the emission processes. On radiating the sample, we could
witness net absorption proportional to the population difference (N1 N2) between the lower and
upper levels. That is , the net rate of energy exchange (in fact it may be the energy extraction!!)
basically from the incident electromagnetic radiation (electromagnetic field) by the molecular
sample is proportional to the population difference (N1 N2) between the two states involved in
the transition. If the molecular sample system is in thermal equilibrium at a temperature T, the
relative populations of the upper and lower energy levels are governed by the Boltzmann
distribution law:

( )

For electronic transitions and virtually all vibrational transitions the upper energy level is
virtually unpopulated at normal temperatures (18 - 38 C), only net absorption processes are
significant.

An interesting point to note is that it is also possible to facilitate a potential non-equilibrium

distribution of molecules between the upper and lower levels with the upper level’s population
(N2), is greater than the lower level’s population (N1). This phenomenon is called as population
inversion. When such an assembly of molecules is irradiated with light of the appropriate
frequency, stimulated emission process with coherent emission of photons along the direction of
transmitted radiation is observed and thus, the initial electromagnetic radiation (i.e., the
incident radiation) is amplified in intensity significantly due to the coherence of the process,
which is very much exploited in the generation of LASER radiation.

Selection Rules
Now that we have learnt that the intensity of the transition between the lower level (initial state)
and the upper level (final state) is proportional to |μ12|2 (square modulus of the transition
integral or transition dipole moment). We can decide whether or not a particular transition can
occur in the spectrum (i.e., whether |μ12| is non-zero or zero!) by examining the selection rule
for the transition integral or transition dipole moment. In spectroscopy, not all transitions
between states are allowed. The selection rules for electric dipole moment transitions, the rules
that specify the specific transitions that may occur, are based on a close examination of the
transition dipole moment integral between two states of interest. They are established by
identifying the specific conditions under which the transition dipole moment integral (|μ12|) is
non-zero, corresponding to an allowed transition or |μ12| = 0 [zero], for a forbidden transition.
The selection rules for absorption as well as emission of electromagnetic radiation are based on
the criteria for this electric dipole transition moment being non-zero. However, we need to
distinguish between two types of selection rules.

Gross selection rules are descriptions about the physicochemical properties that a molecule
must possess in order to interact and concomitantly capable of exhibiting a particular type of
spectroscopic transition.

Specific selection rules are statements about the changes in specific quantum numbers that
may occur during such a spectroscopic transition.