On the physical interpretation of through-bond interactions: A coupled-chromophore model for π-electron photoionization of non-conjugated dienes

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.