Physics – Chemical Physics
Scientific paper
2004-10-26
Physics
Chemical Physics
To appear in Physical Review B, vol 70, 15 Oct 2004
Scientific paper
10.1103/PhysRevB.70.205204
This paper presents a possible explanation for the enhanced singlet exciton yield in light emitting polymers. We propose a theory of electron-hole recombination via inter-molecular inter-conversion from inter-molecular weakly bound polaron pairs (or charge-transfer excitons) to intra-molecular excitons. This theory is applicable to parallel polymer chains. A crucial aspect of the theory is that both the intra-molecular and inter-molecular excitons are effective-particles, which are described by both a relative-particle wavefunction and a center-of-mass wavefunction. This implies two electronic selection rules. (1) The parity of the relative-particle wavefunction implies that inter-conversion occurs from the even parity inter-molecular charge-transfer excitons to the strongly bound intra-molecular excitons. (2) The orthonormality of the center-of-mass wavefunctions ensures that inter-conversion occurs from the charge-transfer excitons to the lowest branch of the strongly bound exciton families, and not to higher lying members of these families. The inter-conversion is then predominately a multi-phonon process, determined by the Franck-Condon factors. These factors are exponentially smaller for the triplet manifold than the singlet manifold because of the large exchange energy.
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