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Rigorous Franck–Condon absorption and emission spectra of conjugated oligomers from quantum chemistry

J. Chem. Phys. 113, 11372 (2000); doi:10.1063/1.1328067

Issue Date: 22 December 2000

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Stoyan Karabunarliev
Department of Chemistry, University of Houston, Houston, Texas 77204-5641

Martin Baumgarten
Max-Planck-Institut für Polymerforschung, Ackermannweg 10, D-55128 Mainz, Germany

Eric R. Bittner
Department of Chemistry, University of Houston, Houston, Texas 77204-5641

Klaus Müllen
Max-Planck-Institut für Polymerforschung, Ackermannweg 10, D-55128 Mainz, Germany
A harmonic Condon approach is used to calculate excitation and emission band shapes for the lowest dipole-allowed electronic transitions in conjugated oligomers: polyenes, oligorylenes, and para-phenylenevinylenes. Ground- and excited-state adiabatic energies, equilibrium structures, and vibrational modes are obtained within standard all-valence-electron molecular Hamiltonian incorporating extended configuration interaction. The interstate distortion is cast in normal coordinates and used to calculate transition probabilities from the zero-phonon initial state to the vibrational manifold of the final state. Spectral profiles are obtained as a superposition of Lorentzian line shapes. Theoretical band shapes reproduce prominent features in the absorption and fluorescence spectra of the oligomers in question. The strength of the bond-stretching vibronic progression increases with oligomeric length in polyenes, but decreases in para-phenylenevinylenes. In line with experiment, absorption and emission band shapes of para-phenylenevinylenes are obtained intrinsically nonsymmetric due to stiffening of the accepting vibrational modes in the excited state. The Stokes shifts of the apparent 0-0 features in the latter are reproduced and traced back to relaxations in slow, ring-torsional motions. ©2000 American Institute of Physics.
History: Received 1 August 2000; accepted 2 October 2000
Permalink: http://link.aip.org/link/?JCPSA6/113/11372/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.70.Ca
    Molecular properties and interactions with photons Intensities and shapes of molecular spectral lines and bands Oscillator and band strengths, lifetimes, transition moments, and Franck–Condon factors
  • 33.70.Jg
    Molecular properties and interactions with photons Intensities and shapes of molecular spectral lines and bands Line and band widths, shapes, and shifts
  • 33.15.Mt
    Molecular properties and interactions with photons Properties of molecules and molecular ions Rotation, vibration, and vibration–rotation constants
  • 33.20.Tp
    Molecular properties and interactions with photons Molecular spectra Vibrational analysis
  • 33.50.Dq
    Molecular properties and interactions with photons Fluorescence and phosphorescence; radiationless transitions, quenching (intersystem crossing, internal conversion) Fluorescence and phosphorescence spectra
  • 31.50.+w
    Electronic structure of atoms, molecules and their ions: theory Excited states
  • 31.25.Qm
    Electronic structure of atoms, molecules and their ions: theory Electron correlation calculations for atoms and molecules Electron correlation calculations for polyatomic molecules
  • YEAR: 2000

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PUBLICATION DATA

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