Energy of Excimer Luminescence. I. A Reconsideration of Excimer Processes

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Abstract
The interpretation of the energies of excimer luminescence of some polyacenes is considered and it is shown that neither simple molecular exciton attitudes nor charge resonance attitudes can provide satisfactory agreement with experiment. The D2k excimer formed from D2h aromatics is investigated and it is shown that the zeroth‐order dimeric B3g state of 1La parentage may configurationally interact with the zeroth‐order dimeric B3g state of charge resonance nature. The interaction of zeroth‐order dimeric B2u states of 1La and charge resonance parentage is shown to be negligible. It is further suggested that the B3g interaction may be of sufficient magnitude to make experiment and theory compatible. The excimer fluorescences of benzene and phenanthrene have been investigated and established. A review of the data thereby provided, as well as other data in the literature, necessitates that the criteria relevant to excimer formation and luminescence given by Förster be modified. A number of other topics, including a few rather general group theoretic theorems relating to excimer formation, are briefly discussed.

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