Abstract
A coupled-chromophore model is presented to explain the splittings of the photoelectron energies arising in the photoionization of the π-electrons in non-conjugated dienes. The predictions of the model are consistent with the experimental splittings for a range of dienes, and suggest that the σ framework plays no physical role in coupling the two chromophores. The implications for the physical interpretation in terms of through-bond interactions are discussed.
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