Vibronic coupling in the ground state of oligoacene cations: The performance of range-separated hybrid density functionals

Cai Rong Zhang, Veaceslav Coropceanu*, John S. Sears, Jean-Luc Bredas

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

10 Scopus citations


Oligoacenes such as naphthalene, anthracene, tetracene, and pentacene are among the best hole-transport organic semiconductors. An important parameter in the determination of the hole mobility is the coupling between the charge carrier and the vibrational modes. Here, we have evaluated the hole-vibration coupling constants in the radical-cation ground state of these molecules by means of the range-separated LC-ωPBE and ωB97 density functionals, with non-empirical optimization of the range-separation parameter ω. Our results indicate that both ω-tuned functionals yield similar relaxation energies and coupling constants. A comparison of the simulated vibrational structures of the first ionization band to the gas-phase ultraviolet photoelectron spectroscopy data underlines that the hole-vibration coupling constants derived by means of the non-empirically tuned LC-ωPBE and ωB97 functionals are in excellent agreement with experiment and superior to those derived from B3LYP calculations.

Original languageEnglish (US)
Pages (from-to)154-158
Number of pages5
JournalJournal of Physical Chemistry C
Issue number1
StatePublished - Jan 9 2014

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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