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Nonadiabatic quantum dynamics based on a hierarchical electron-phonon model: Exciton dissociation in semiconducting polymers

J. Chem. Phys. 127, 034706 (2007); doi:10.1063/1.2748050

Published 19 July 2007

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Hiroyuki Tamura
Département de Chimie, Ecole Normale Supérieure, 24 Rue Lhomond, F-75231 Paris Cedex 05, France

Eric R. Bittner
Department of Chemistry, University of Houston, Houston, Texas 77204 and Texas Center for Superconductivity, University of Houston, Houston, Texas 77204

Irene Burghardt
Département de Chimie, Ecole Normale Supérieure, 24 Rue Lhomond, F-75231 Paris Cedex 05, France
A hierarchical electron-phonon coupling model is applied to describe the ultrafast decay of a photogenerated exciton at a donor-acceptor polymer heterojunction, via a vibronic coupling mechanism by which a charge-localized interfacial state is created. Expanding upon an earlier Communication [H. Tamura et al., J. Chem. Phys. 126, 021103 (2007)], we present a quantum dynamical analysis based on a two-state linear vibronic coupling model, which accounts for a two-band phonon bath including high-frequency C[Double Bond]C stretch modes and low-frequency ring torsional modes. Building upon this model, an analysis in terms of a hierarchical chain of effective modes is carried out, whose construction is detailed in the present paper. Truncation of this chain at the order n (i.e., 3n+3 modes) conserves the Hamiltonian moments (cumulants) up to the (2n+3)rd order. The effective-mode analysis highlights (i) the dominance of the high-frequency modes in the coupling to the electronic subsystem and (ii) the key role of the low-frequency modes in the intramolecular vibrational redistribution process that is essential in mediating the decay to the charge-localized state. Due to this dynamical interplay, the effective-mode hierarchy has to be carried beyond the first order in order to obtain a qualitatively correct picture of the nonadiabatic process. A reduced model of the dynamics, including a Markovian closure of the hierarchy, is presented. Dynamical calculations were carried out using the multiconfiguration time-dependent Hartree method. ©2007 American Institute of Physics
History: Received 8 March 2007; accepted 16 May 2007; published 19 July 2007
Permalink: http://link.aip.org/link/?JCPSA6/127/034706/1
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KEYWORDS and PACS

Keywords
PACS
  • 71.35.-y
    Excitons and related phenomena
  • 71.38.-k
    Polarons and electron–phonon interactions
  • 63.50.+x
    Vibrational states in disordered systems
  • 73.20.Mf
    Collective excitations (surface/interface states) including excitons, polarons, plasmons and other charge-density excitations
  • 73.40.Lq
    Electrical properties of other semiconductor-to-semiconductor contacts, p–n junctions, and heterojunctions excluding III–V semiconductor-to-semiconductor
  • 72.80.Le
    Electrical conductivity of polymers; organic compounds including organic semiconductors
  • YEAR: 2007

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PUBLICATION DATA

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