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Title: Characterization of the quasi-one-dimensional compounds δ-(EDT-TTF-CONMe{sub 2}){sub 2}X, X=AsF{sub 6} and Br by vibrational spectroscopy and density functional theory calculations

We have investigated the infrared spectra of the quarter-filled charge-ordered insulators δ-(EDT-TTF-CONMe{sub 2}){sub 2}X (X= AsF{sub 6}, Br) along all three crystallographic directions in the temperature range from 300 to 10 K. DFT-assisted normal mode analysis of the neutral and ionic EDT-TTF-CONMe{sub 2} molecule allows us to assign the experimentally observed intramolecular modes and to obtain relevant information on the charge ordering and intramolecular interactions. From frequencies of charge-sensitive vibrations we deduce that the charge-ordered state is already present at room temperature and does not change on cooling, in agreement with previous NMR measurements. The spectra taken along the stacking direction clearly show features of vibrational overtones excited due to the anharmonic electronic molecule potential caused by the large charge disproportionation between the molecular sites. The shift of certain vibrational modes indicates the onset of the structural transition below 200 K.
Authors:
;  [1] ;  [1] ;  [2] ;  [3] ;  [1] ;  [4]
  1. 1. Physikalisches Institut, Universität Stuttgart, Pfaffenwaldring 57, 70550 Stuttgart (Germany)
  2. (EPFL), 1015 Lausanne (Switzerland)
  3. Laboratoire MOLTECH, UMR 6200 CNRS-Université d'Angers, Bt. K, UFR Sciences, 2 Boulevard Lavoisier, F-49045 Angers (France)
  4. (United States)
Publication Date:
OSTI Identifier:
22255123
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 6; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CRYSTALLOGRAPHY; DENSITY FUNCTIONAL METHOD; INFRARED SPECTRA; INTERACTIONS; NORMAL-MODE ANALYSIS; NUCLEAR MAGNETIC RESONANCE; OXIDATION; SPECTROSCOPY