Microscopic origin of the charge transfer in single crystals based on thiophene derivatives: A combined NEXAFS and density functional theory approach

Research output: Contribution to journalArticle


We have investigated the charge transfer mechanism in single crystals of DTBDT-TCNQ and DTBDT-F4TCNQ (where DTBDT is dithieno[2,3-d;2′,3′-d′] benzo[1,2-b;4,5-b′]dithiophene) using a combination of near-edge X-ray absorption spectroscopy (NEXAFS) and density functional theory calculations (DFT) including final state effects beyond the sudden state approximation. In particular, we find that a description that considers the partial screening of the electron-hole Coulomb correlation on a static level as well as the rearrangement of electronic density shows excellent agreement with experiment and allows to uncover the details of the charge transfer mechanism in DTBDT-TCNQ and DTBDT-F4 TCNQ, as well as a reinterpretation of previous NEXAFS data on pure TCNQ. Finally, we further show that almost the same quality of agreement between theoretical results and experiment is obtained by the much faster Z+1/2 approximation, where the core hole effects are simulated by replacing N or F with atomic number Z with the neighboring atom with atomic number Z+1/2.


  • A. Chernenkaya
  • A. Morherr
  • S. Backes
  • W. Popp
  • S. Witt
  • X. Kozina
  • S. A. Nepijko
  • M. Bolte
  • K. Medjanik
  • G. Öhrwall
  • C. Krellner
  • M. Baumgarten
  • H. J. Elmers
  • G. Schönhense
  • H. O. Jeschke
  • R. Valentí
External organisations
  • University of Mainz
  • Goethe University
  • Max Planck Institute for Polymer Research
Research areas and keywords

Subject classification (UKÄ) – MANDATORY

  • Physical Chemistry
Original languageEnglish
Article number034702
JournalJournal of Chemical Physics
Issue number3
Publication statusPublished - 2016 Jul 21
Publication categoryResearch