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    Kasha's Rule - Wikipedia

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    Sheetal Thakur
    Kasha's rule states that photon emission, such as fluorescence or phosphorescence, occurs most readily from the lowest excited state of a molecule. Upon absorbing a photon, a molecule will quickly relax to its lowest excited state through internal conversion before emitting a photon. This explains why the emission spectrum of an excited molecule is generally independent of the excitation wavelength. Exceptions can occur when there is a large energy gap between excited states that prevents rapid internal conversion.

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    Kasha's Rule - Wikipedia

    Uploaded by

    Sheetal Thakur
    108 views7 pages
    Kasha's rule states that photon emission, such as fluorescence or phosphorescence, occurs most readily from the lowest excited state of a molecule. Upon absorbing a photon, a molecule will quickly relax to its lowest excited state through internal conversion before emitting a photon. This explains why the emission spectrum of an excited molecule is generally independent of the excitation wavelength. Exceptions can occur when there is a large energy gap between excited states that prevents rapid internal conversion.

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    Kasha's rule states that photon emission, such as fluorescence or phosphorescence, occurs most readily from the lowest excited state of a molecule. Upon absorbing a photon, a molecule will quickly relax to its lowest excited state through internal conversion before emitting a photon. This explains why the emission spectrum of an excited molecule is generally independent of the excitation wavelength. Exceptions can occur when there is a large energy gap between excited states that prevents rapid internal conversion.

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
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    108 views7 pages

    Kasha's Rule - Wikipedia

    Uploaded by

    Sheetal Thakur
    Kasha's rule states that photon emission, such as fluorescence or phosphorescence, occurs most readily from the lowest excited state of a molecule. Upon absorbing a photon, a molecule will quickly relax to its lowest excited state through internal conversion before emitting a photon. This explains why the emission spectrum of an excited molecule is generally independent of the excitation wavelength. Exceptions can occur when there is a large energy gap between excited states that prevents rapid internal conversion.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
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    of 7

    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.

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