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Kasha's rule: a reappraisal.

Juan Carlos Del Valle1, Javier Catalán

  • 1Departamento de Química Física Aplicada, Universidad Autónoma de Madrid, C-2-203. E-28049, Cantoblanco, Madrid, Spain. Juan.valle@uam.es Javier.catalan@uam.es.

Physical Chemistry Chemical Physics : PCCP
|May 4, 2019
PubMed
Summary

This study revises cases that appear to violate Kasha's rule in photophysics. Findings confirm that most molecules adhere to Kasha's rule, stating emission originates from the lowest excited electronic level of a given multiplicity.

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Area of Science:

  • Photophysics and Molecular Spectroscopy
  • Quantum Chemistry

Background:

  • Kasha's rule is a fundamental principle in photophysics.
  • It states that emission originates from the lowest excited electronic state of a given spin multiplicity.
  • Some literature cases appear to contradict this rule.

Purpose of the Study:

  • To re-evaluate literature cases that seemingly violate Kasha's rule.
  • To clarify the applicability of Kasha's rule in complex molecular systems.
  • To provide accurate photophysical interpretations.

Main Methods:

  • Literature review and critical analysis of reported anomalous cases.
  • Theoretical examination of electronic transitions and relaxation pathways.
  • Comparison with the precise statement of Kasha's rule.

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Main Results:

  • Most molecules examined comply with Kasha's rule.
  • Azulene is identified as a notable exception.
  • The analysis reinforces the validity of Kasha's rule under specified conditions.

Conclusions:

  • The apparent violations of Kasha's rule are often due to misinterpretations or imprecise statements of the rule.
  • Kasha's rule remains a robust principle governing fluorescence and phosphorescence.
  • Accurate understanding of molecular photophysics requires careful consideration of electronic states and relaxation processes.