Microscopic origin of the charge transfer in single crystals based on thiophene derivatives

A combined NEXAFS and density functional theory approach

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, Harald Olaf Jeschke, R. Valentí

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

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-F4TCNQ, 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.

Original languageEnglish
Article number034702
JournalJournal of Chemical Physics
Volume145
Issue number3
DOIs
Publication statusPublished - Jul 21 2016
Externally publishedYes

Fingerprint

Thiophenes
thiophenes
Density functional theory
Charge transfer
charge transfer
Single crystals
density functional theory
Derivatives
single crystals
approximation
absorption spectroscopy
X ray absorption spectroscopy
screening
Screening
Experiments
electronics
atoms
Atoms
x rays
Electrons

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Microscopic origin of the charge transfer in single crystals based on thiophene derivatives : A combined NEXAFS and density functional theory approach. / Chernenkaya, A.; Morherr, A.; Backes, S.; Popp, W.; Witt, S.; Kozina, X.; Nepijko, S. A.; Bolte, M.; Medjanik, K.; Öhrwall, G.; Krellner, C.; Baumgarten, M.; Elmers, H. J.; Schönhense, G.; Jeschke, Harald Olaf; Valentí, R.

In: Journal of Chemical Physics, Vol. 145, No. 3, 034702, 21.07.2016.

Research output: Contribution to journalArticle

Chernenkaya, A, Morherr, A, Backes, S, Popp, W, Witt, S, Kozina, X, Nepijko, SA, Bolte, M, Medjanik, K, Öhrwall, G, Krellner, C, Baumgarten, M, Elmers, HJ, Schönhense, G, Jeschke, HO & Valentí, R 2016, 'Microscopic origin of the charge transfer in single crystals based on thiophene derivatives: A combined NEXAFS and density functional theory approach', Journal of Chemical Physics, vol. 145, no. 3, 034702. https://doi.org/10.1063/1.4958659
Chernenkaya, A. ; Morherr, A. ; Backes, S. ; Popp, W. ; Witt, S. ; Kozina, X. ; Nepijko, S. A. ; Bolte, M. ; Medjanik, K. ; Öhrwall, G. ; Krellner, C. ; Baumgarten, M. ; Elmers, H. J. ; Schönhense, G. ; Jeschke, Harald Olaf ; Valentí, R. / Microscopic origin of the charge transfer in single crystals based on thiophene derivatives : A combined NEXAFS and density functional theory approach. In: Journal of Chemical Physics. 2016 ; Vol. 145, No. 3.
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