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 language | English |
|---|---|
| Article number | 034702 |
| Journal | Journal of Chemical Physics |
| Volume | 145 |
| Issue number | 3 |
| DOIs | |
| Publication status | Published - Jul 21 2016 |
| Externally published | Yes |
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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 journal › Article
}
TY - JOUR
T1 - Microscopic origin of the charge transfer in single crystals based on thiophene derivatives
T2 - A combined NEXAFS and density functional theory approach
AU - Chernenkaya, A.
AU - Morherr, A.
AU - Backes, S.
AU - Popp, W.
AU - Witt, S.
AU - Kozina, X.
AU - Nepijko, S. A.
AU - Bolte, M.
AU - Medjanik, K.
AU - Öhrwall, G.
AU - Krellner, C.
AU - Baumgarten, M.
AU - Elmers, H. J.
AU - Schönhense, G.
AU - Jeschke, Harald Olaf
AU - Valentí, R.
PY - 2016/7/21
Y1 - 2016/7/21
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84979294595&partnerID=8YFLogxK
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U2 - 10.1063/1.4958659
DO - 10.1063/1.4958659
M3 - Article
VL - 145
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 3
M1 - 034702
ER -