Electronic Couplings in Organic Mixed-Valence Compounds: The Contribution of Photoelectron Spectroscopy

Veaceslav Coropceanu, Nadine E. Gruhn, Stephen Barlow, Christoph Lambert, Jason C. Durivage, Tonja G. Bill, Gilbert Nöll, Seth R. Marder, Jean Luc Brédas

Research output: Contribution to journalArticlepeer-review

80 Scopus citations


We show that the electronic coupling in strongly coupled organic mixed-valence systems can be effectively probed by means of gas-phase ultraviolet photoelectron spectroscopy (UPS). Taking six diamines as examples, the UPS estimates for the electronic couplings Hab are compared with the corresponding values determined from the intervalence charge-transfer absorption bands and from electronic structure calculations. Similar trends are observed for the Hab values estimated from UPS and optical spectra; this provides support for the applicability of Hush theory to strongly coupled organic mixed-valence systems. The UPS electronic couplings are found to be somewhat smaller than those from optical spectroscopy, which is attributed to the role of vibronic coupling to symmetrical modes; when corrected for this vibronic coupling, the UPS Hab estimates confirm that triarylamine-based mixed-valence systems are close to the class-II/class-III borderline.

Original languageEnglish (US)
Pages (from-to)2727-2731
Number of pages5
JournalJournal of the American Chemical Society
Issue number9
StatePublished - Mar 10 2004
Externally publishedYes

ASJC Scopus subject areas

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


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