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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. LU and Öhrwall, G. LU , et al. (2016) In Journal of Chemical Physics 145(3).
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-F4 TCNQ, as well as a reinterpretation... (More)

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.

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Journal of Chemical Physics
volume
145
issue
3
publisher
American Institute of Physics
external identifiers
  • scopus:84979294595
  • wos:000381384300038
ISSN
0021-9606
DOI
10.1063/1.4958659
language
English
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yes
id
72725782-cffd-4612-8a81-4b4431281abd
date added to LUP
2017-01-10 10:27:41
date last changed
2017-09-18 11:35:35
@article{72725782-cffd-4612-8a81-4b4431281abd,
  abstract     = {<p>We have investigated the charge transfer mechanism in single crystals of DTBDT-TCNQ and DTBDT-F<sub>4</sub>TCNQ (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-F<sub>4</sub> 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.</p>},
  articleno    = {034702},
  author       = {Chernenkaya, A. and Morherr, A. and Backes, S. and Popp, W. and Witt, S. and Kozina, X. and Nepijko, S. A. and Bolte, M. and Medjanik, K. and Öhrwall, G. and Krellner, C. and Baumgarten, M. and Elmers, H. J. and Schönhense, G. and Jeschke, H. O. and Valentí, R.},
  issn         = {0021-9606},
  language     = {eng},
  month        = {07},
  number       = {3},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Microscopic origin of the charge transfer in single crystals based on thiophene derivatives : A combined NEXAFS and density functional theory approach},
  url          = {http://dx.doi.org/10.1063/1.4958659},
  volume       = {145},
  year         = {2016},
}