Spin-dependent electron-hole capture kinetics in conjugated polymers

The recombination of electron-hole pairs injected in extended conjugated systems is modeled as a multi-pathway vibron-driven relaxation in monoexcited state-space. The computed triplet-to-singlet ratio of exciton formation times $r = \tau_T/\tau_S$ increases from 0.9 for a model dimer to 2.5 for a 32-unit chain, in excellent agreement with experiments. Therewith we rationalize recombination efficiency in terms of spin-dependent interstate vibronic coupling and spin- and conjugation-length-dependent exciton binding energies.Our model calculations for various length polymers indicate that the ratio of the singlet to triplet formation ratios, $r = \sigma_S/\sigma_T$, is inversely related to the ratio of the singlet and triplet binding energies, $\epsilon^b_S/\epsilon^b_T$.