Laporte rule

The Laporte rule is a rule that explains the intensities of absorption spectra for chemical species. It is a selection rule that rigorously applies to atoms, and to molecules that are centrosymmetric, i.e. with an inversion centre. It states that electronic transitions that conserve parity are forbidden. Thus transitions between two states that are each symmetric with respect to an inversion centre will not be observed. Transitions between states that are antisymmetric with respect to inversion are forbidden as well. In the language of symmetry, g (gerade = even (German)) → g and u (ungerade = odd) → u transitions are forbidden. Allowed transitions must involve a change in parity, either gu or ug.

For atoms s and d orbitals are gerade, and p and f orbitals are ungerade. The Laporte rule implies that s to s, p to p, d to d, etc. transitions should not be observed in atoms or centrosymmetric molecules. Practically speaking, only d-d transitions occur in the visible region of the spectrum. The Laporte rule is most commonly discussed in the context of the electronic spectroscopy of transition metal complexes. However, low-intensity f-f transitions in the actinide elements can be observed in the near-infrared region.[1][2]

  1. ^ Cary, Samantha K.; Vasiliu, Monica; Baumbach, Ryan E.; Stritzinger, Jared T.; Green, Thomas D.; Diefenbach, Kariem; Cross, Justin N.; Knappenberger, Kenneth L.; Liu, Guokui; Silver, Mark A.; DePrince, A. Eugene; Polinski, Matthew J.; Van Cleve, Shelley M.; House, Jane H.; Kikugawa, Naoki (2015-04-16). "Emergence of californium as the second transitional element in the actinide series". Nature Communications. 6 (1): 6827. doi:10.1038/ncomms7827. ISSN 2041-1723. PMC 4410632. PMID 25880116.
  2. ^ Wolford, Nikki J.; Yu, Xiaojuan; Bart, Suzanne C.; Autschbach, Jochen; Neidig, Michael L. (2020-10-27). "Ligand effects on electronic structure and bonding in U(III) coordination complexes: a combined MCD, EPR and computational study". Dalton Transactions. 49 (41): 14401–14410. doi:10.1039/D0DT02929G. ISSN 1477-9234. OSTI 1850721. PMID 33001085. S2CID 222172077.

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