CHM3105 Short Paper

Name: Trimal Accra

USI: 1032430
Lecturer: Mr. Samuel Lee

The Franck-Condon Principle and its application related to distribution of intensities

The intensity of vibronic transitions, or the absorption or emission of a photon, is described

by the Franck-Condon Principle. It states that when a molecule undergoes an electronic
transition, such as ionization, the molecule's nuclear configuration remains unchanged. This
is because nuclei have a significantly larger mass than electrons, and the electronic transition
occurs faster than the nuclei can respond. According to the notion, when the nucleus realigns
itself with the new electrical arrangement, it must vibrate.

Franck–Condon principle energy diagram.

In the diagram above we the vibronic transition is illustrated by the blue and green vertical
arrows on the nuclear axis as a result of the internuclear separation. Three things are
demonstrated in this diagram:
 Fluorescence leads to a lower energy state
 An absorption leads to a higher energy state
 The change in nuclear coordinates between the ground and excited states indicates a
new nuclear interaction potential equilibrium position. The fluorescence arrow is
shorter than the absorption arrow, indicating that it has less energy or a longer
wavelength.

The Condon approximation assumes that the electronic transition takes place on a shorter
time scale than nuclear mobility, allowing the transition probability to be estimated at a fixed
nuclear location. This vibrational shift is sustained in a state known as rapid electronic
excitation. The ensuing Coulombic forces establish an equilibrium, which is referred to as a
turning point, as illustrated in the figure for the nuclei. A vertical line drawn from the
minimum of the lower curve to the junction of the upper electronic state can be used to map
the turning point. A vertical transition is a process that was previously explored in the context
of photoelectron spectroscopy (another electronic spectroscopy).

By connecting the probablity of a vibrational transition to the overlap of the vibrational wave
functions, the Franck-Condon Principle explains the relative intensities of vibronic
transitions. The Franck-Condon overlap integral is used to weight the probability of a
vibrational transition occurring:

Pi→f=|⟨ψ∗final|μ|ψinitial⟩|2=|∫ψ∗finalμψinitialdτ|2

During electronic transitions, the nuclei are regarded "stationary" under the Franck-Condon
approximation. Electronic transitions can therefore be thought of as vertical changes on
electronic potential energy curves (as seen in the diagram above).

The Franck-Condon Principle has both a Classical and Quantum application. Classically, the
Franck–Condon principle is the approximation that an electronic transition is most likely to
occur without changes in the positions of the nuclei in the molecular entity and its
environment. The resulting state is called a Franck–Condon state, and the transition involved,
a vertical transition. The quantum mechanical formulation of this principle is that the
intensity of a vibronic transition is proportional to the square of the overlap integral between
the vibrational wavefunctions of the two states that are involved in the transition
(Ziering.M,Franzen.S,2022)

In a report published in 1926 in Transactions of the Faraday Society, James Franck was
concerned with the mechanisms of photon-induced chemical reactions. A photon was thought
to excite a molecule, which was then followed by a collision with another molecule during
the short time of excitation. The question was whether a molecule might break down into
photoproducts in a single step, without colliding, by absorption of a photon. To break apart, a
molecule must obtain from the photon a vibrational energy greater than the dissociation
energy, or the energy required to dissolve a chemical bond. However, molecules will only
absorb energy matching to allowable quantum transitions, and there are no vibrational levels
above the potential well's dissociation energy level, as was understood at the time. Instead of
dissociation, high-energy photon absorption causes a shift to a higher electronic state. He
drew three diagrams representing the possible changes in binding energy between the lowest
electronic state and higher electronic states to investigate how much vibrational energy a
molecule could acquire when it is excited to a higher electronic level, and whether this
vibrational energy could be enough to break the molecule apart immediately. Changes in
vibrational levels could be a result of the instantaneous nature of excitation to higher
electronic energy levels, as well as a new equilibrium point for the nuclear interaction
potential, according to James Franck. In a 1926 Physical Review paper titled "A Theory of
Intensity Distribution in Band Systems," Edward Condon extended this idea beyond
photoreactions. [2] He formulates the semiclassical formulation in a manner that is very
similar to its present version in this section. In the same 1926 edition of Physical Review, an
article on the band structure of carbon monoxide by Raymond Birge makes the first joint
reference to both Franck and Condon in relation to the new principle.

Reference:
Ziering.M,Franzen.S (2022). The Franck-Condon Principle. Retrieved from:
https://chem.libretexts.org/Courses/Pacific_Union_College/Quantum_Chemistry/
13%3A_Molecular_Spectroscopy/13.07%3A_The_Franck-Condon_Principle