Fine structure of triplet exciton polarons in polydiacetylene molecules

Triplet states on conjugated polydiacetylene chains which are created by UV excitation are examined experimentally using ODMR spectroscopy. The observed fine structure shows that the triplet state can be ascribed to the conjugated chain rather than to the side groups and that it is localized. This leads to the suggestion of an exciton polaron. In the theoretical part the wave function of the exciton polaron is calculated using the configuration model in analogy to the description of pz radical electrons on carbene chain ends of reactive short‐chain intermediates. The total fine structure tensor is obtained by summing up the fine structure tensors of the individual configurations weighted by their probability densities. The transfer integral t of the configuration model is fitted with respect to good agreement between experimentally observed and calculated fine structure parameters. Finally, comparison between the experimentally observed ESR linewidth and the calculated hyperfine structure splitting shows ...