Toward a robust quantum-chemical description of organic mixed-valence systems

Christopher Sutton, Thomas Körzdörfer, Veaceslav Coropceanu, Jean-Luc Bredas*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

23 Scopus citations

Abstract

The electronic coupling between redox sites in mixed-valence systems has attracted the interest of the chemistry community for a long time. Many computational studies have focused on trying to determine its magnitude as a function of the nature of the redox sites and of the bridge(s) between them. However, in most instances, the quantum-chemical methodologies that have been employed suffer from intrinsic errors that lead to either an overlocalized or an overdelocalized character of the electronic structure. These deficiencies prevent an accurate depiction of the degree of charge (de)localization in the system and, as a result, of the extent of electronic coupling. Here we use nonempirically tuned long-range corrected density functional theory and show that it provides a robust, efficient approach to characterize organic mixed-valence systems. We first demonstrate the performance of this approach via a study of representative Robin-Day class-II (localized) and class-III (delocalized) complexes. We then examine a borderline class-II/class-III complex, which had proven difficult to describe accurately with standard density functional theory and Hartree-Fock methods.

Original languageEnglish (US)
Pages (from-to)3925-3934
Number of pages10
JournalJournal of Physical Chemistry C
Volume118
Issue number8
DOIs
StatePublished - Feb 27 2014

ASJC Scopus subject areas

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

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