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On the nature of electronic excitations in poly(paraphenylenevinylene): A quantum-chemical investigation

J. Chem. Phys. 111, 2829 (1999); doi:10.1063/1.479560

Issue Date: 8 August 1999

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D. Beljonne, Z. Shuai, J. Cornil, D. A. dos Santos, and J. L. Brédas
Laboratory for Chemistry of Novel Materials, Center for Research in Molecular Electronics and Photonics, University of Mons-Hainaut, 20, Place du Parc, B-7000 Mons, Belgium
Correlated quantum-chemical calculations are performed on phenylenevinylene oligomers containing up to eleven repeat units, to characterize the nature of the electronic excitations relevant for the photophysical properties of the corresponding polymer. The focus is first on the nonlinear optical response of model conjugated chains and the simulation of their frequency-dependent (third-harmonic generation, electroabsorption, and two-photon absorption) response. From the assignment of the calculated resonance features, the excited states dominating the third-order nonlinear polarizability are identified and their chain-length dependence is investigated. On that basis, we build an essential-state single-chain model (that includes the 1Bu, 2Ag, mAg, and nBu states) and apply it to the interpretation of recent experimental data reported for poly(paraphenylenevinylene) and derivatives. We then examine how the exciton binding energy, here defined as the difference between the energies of the charge-separated nBu and the strongly optically allowed 1Bu excited states, is affected by both intrachain and interchain polarization effects. ©1999 American Institute of Physics.
History: Received 1 March 1999; accepted 11 May 1999
Permalink: http://link.aip.org/link/?JCPSA6/111/2829/1
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KEYWORDS and PACS

Keywords
PACS
  • 42.65.Ky
    Optics Nonlinear optics Harmonic generation, frequency conversion
  • 78.20.Jq
    Optical properties, condensed-matter spectroscopy and other interactions of radiation and particles with condensed matter Optical properties of bulk materials and thin films Electrooptical effects
  • 42.65.An
    Optics Nonlinear optics Optical susceptibility, hyperpolarizability
  • YEAR: 1999

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PUBLICATION DATA

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