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Dissipative dynamics of spin-dependent electron–hole capture in conjugated polymers

J. Chem. Phys. 119, 3988 (2003); doi:10.1063/1.1591719

Issue Date: 15 August 2003

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Stoyan Karabunarliev and Eric R. Bittner
Department of Chemistry and Center for Materials Chemistry, University of Houston, Houston, Texas 77204-5003
Spin-dependent electron–hole (e–h) recombination in poly(p-phenylenevinylene) chains is modeled by the dissipative dynamics of the multilevel electronic system coupled to the phonon bath. The underlying Hamiltonian incorporates the Coulomb and exchange interactions of spin-singlet and spin-triplet monoexcitations in Wannier-orbital basis and their coupling to the prominent Franck–Condon active modes. In agreement with experiment, we obtain that the ratio of singlet versus triplet exciton formation rates is strongly conjugation-length dependent and increasing on going from the model dimer to the extended chain. The result is rationalized in terms of a cascade interconversion mechanism across the electronic levels. In parallel to the direct formation of spin-dependent excitons, e–h capture is found to generate long-lived charge-transfer states, whose further phonon-mediated relaxation to the bottom of the density of states is hindered by the near e–h symmetry of conjugated hydrocarbons. Being nearly spin independent, such states most likely form an intersystem crossing pre-equilibrium, from which the singlet e–h binding channel is about ten times faster than the triplet one. ©2003 American Institute of Physics.
History: Received 19 February 2003; accepted 21 May 2003
Permalink: http://link.aip.org/link/?JCPSA6/119/3988/1
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KEYWORDS and PACS

Keywords
PACS
  • 72.80.Le
    Electrical conductivity of polymers; organic compounds including organic semiconductors
  • 72.15.Nj
    Collective modes (e.g., in one-dimensional conductors) including synthetic metals
  • YEAR: 2003

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0021-9606 (print)   1089-7690 (online)
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