Singlet-triplet splitting of geminate electron-hole pairs in conjugated polymers

The singlet-triplet splitting of geminate polaron pairs in a ladder-type conjugated polymer has been studied by the thermally stimulated luminescence technique. The energy gap separating the singlet and triplet states of the geminate pairs is measured to be in the range of 3-6 meV, depending on the polymer morphology. The results of correlated quantum-chemical calculations on a long ladder-type oligomer are fully consistent with the observed values of the geminate polaron pair singlet-triplet gap. Such low splitting values have important implications for the spin-dependent exciton formation in conjugated polymers.