Kasha's rule

Kasha's rule is a principle in the

photochemistry of electronically excited
molecules. The rule states that photon
emission (fluorescence
(fluorescence or
phosphorescence)) occurs in appreciable
phosphorescence
yield only from the lowest excited state
of a given multiplicity
multiplicity.. It is named after
American spectroscopist Michael Kasha,
who proposed it in 1950.[1][2]
 Scheme of Kasha's rule. A photon with energy
excites an electron of fundamental level, of
energy , up to an excited energy level (e.g.
or ) or on one of the vibrational sub-levels.
Vibrational relaxation then takes place between
excited levels, which leads to dissipation of part
of the energy ( ), taking the form of a
transition (internal conversion) towards the
lowest excited level. Energy is then dissipated by
emission of a photon of energy , which allows
the system to go back to its fundamental state.

Description and explanation

The rule is relevant in understanding the
emission spectrum of an excited
molecule. Upon absorbing a photon, a
molecule in its electronic ground state
(denoted S0, assuming a singlet state)
may – depending on the photon
wavelength – be excited to any of a set
of higher electronic states (denoted Sn
where n>0). However, according to
Kasha's rule, photon emission (termed
fluorescence in the case of an S state) is
expected in appreciable yield only from
the lowest excited state, S1. Since only
one state is expected to yield emission,
an equivalent statement of the rule is
that the emission wavelength is
independent of the excitation
wavelength.[3]

The rule can be explained by the

Franck–Condon factors for vibronic
transitions. For a given pair of energy
levels that differ in both vibrational and
electronic quantum numbers, the
Franck–Condon factor expresses the
degree of overlap between their
vibrational wavefunctions. The greater
the overlap, the more quickly the
molecule can undergo a transition from
the higher to the lower level. Overlap
between pairs is greatest when the two
vibrational levels are close in energy; this
tends to be the case when the
vibrationless levels of the electronic
states coupled by the transition (where
the vibrational quantum number v is
zero) are close. In most molecules, the
vibrationless levels of the excited states
all lie close together, so molecules in
upper states quickly reach the lowest
excited state, S1, before they have time
to fluoresce. However, the energy gap
between S1 and S0 is greater, so here
fluorescence occurs, since it is now
kinetically competitive with internal
conversion (IC).[4][5]

Exceptions to Kasha's rule arise when

there are large energy gaps between
excited states. An example is azulene:
the classical explanation is that the S1
and S2 states lie sufficiently far apart that
fluorescence is observed mostly from
S2.[4][5] In 2023, an explanation was
proposed which pointed out that the S1
excited state has antiaromatic character
while the S2 excited state is aromatic.[6]

Vavilov rule
A corollary of Kasha's rule is the Vavilov
rule, which states that the quantum yield
of luminescence is generally
independent of the excitation
wavelength.[4][7] This can be understood
as a consequence of the tendency –
implied by Kasha's rule – for molecules
in upper states to relax to the lowest
excited state non-radiatively. Again there
are exceptions: for example benzene
vapour.[4]

See also
Stokes shift, the difference between
the absorption and emission
frequencies, related to Kasha's rule.[8]

References
1. Characterization of Electronic Transitions
in Complex Molecules (https://web.archi
ve.org/web/20020325103542/http://tur
mac13.chem.columbia.edu/PDF_db/His
tory/characterization.PDF) . Kasha, M.
Discussions of the Faraday Society,
1950, 9: p.14-19.