Effect of electronic polarization on charge-transport parameters in molecular organic semiconductors

Edward F. Valeev*, Veaceslav Coropceanu, Demetrio A. Da Silva Filho, Seyhan Salman, Jean Luc Brédas

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

763 Scopus citations


Theoretical investigations of charge transport in organic materials are generally based on the "energy splitting in dimer" method and routinely assume that the transport parameters (site energies and transfer integrals) determined from monomer and dimer calculations can be reliably used to describe extended systems. Here, we demonstrate that this transferability can fail even in molecular crystals with weak van der Waals intermolecular interactions, due to the substantial (but often ignored) impact of polarization effects, particularly on the site energies. We show that the neglect of electronic polarization leads to qualitatively incorrect values and trends for the transfer integrals computed with the energy splitting method, even in simple prototypes such as ethylene or pentacene dimers. The polarization effect in these systems is largely electrostatic in nature and can change dramatically upon transition from a dimer to an extended system. For example, the difference in site energy for a prototypical "face-to-edge" one-dimensional stack of pentacene molecules is calculated to be 30% greater than that in the "face-to-edge" dimer, whereas the site energy difference in the pentacene crystal is vanishingly small. Importantly, when computed directly in the framework of localized monomer orbitals, the transfer integral values for dimer and extended systems are very similar.

Original languageEnglish (US)
Pages (from-to)9882-9886
Number of pages5
JournalJournal of the American Chemical Society
Issue number30
StatePublished - Aug 2 2006
Externally publishedYes

ASJC Scopus subject areas

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry


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