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Electronic structure of thin film iron-tetracyanoethylene: Fe(TCNE)x
Authors:Pramod Bhatt   E. Carlegrim   A. Kanciurzewska   M. P. de Jong  M. Fahlman
Affiliation:1.Department of Physics, Chemistry and Biology,Link?ping University,Link?ping,Sweden;2.Applied Photochemistry Lab, Faculty of Chemistry,Adam Mickiewicz University,Poznań,Poland;3.MESA Institute for Nanotechnology,University of Twente,AE Enschede,The Netherlands
Abstract:
Thin film iron-tetracyanoethylene Fe(TCNE) x , x∼2, as determined by photoelectron spectroscopy, was grown in situ under ultra-high vacuum conditions using a recently developed physical vapor deposition-based technique for fabrication of oxygen- and precursor-free organic-based molecular magnets. Photoelectron spectroscopy results show no spurious trace elements in the films, and the iron is of Fe2+ valency. The highest occupied molecular orbital of Fe(TCNE) x is located at ∼1.7 eV vs. Fermi level and is derived mainly from the TCNE singly occupied molecular orbital according to photoelectron spectroscopy and resonant photoelectron spectroscopy results. The Fe(3d)-derived states appear at higher binding energy, ∼4.5 eV, which is in contrast to V(TCNE)2 where the highest occupied molecular orbital is mainly derived from V(3d) states. Fitting ligand field multiplet and charge transfer multiplet calculations to the Fe L-edge near edge X-ray absorption fine structure spectrum yields a high-spin Fe2+ (3d6) configuration with a crystal field parameter 10Dq∼0.6 eV for the Fe(TCNE) x system. We propose that the significantly weaker Fe-TCNE ligand interaction as compared to the room temperature magnet V(TCNE)2 (10Dq∼2.3 eV) is a strongly contributing factor to the substantially lower magnetic ordering temperature (T C ) seen for Fe(TCNE) x -type magnets.
Keywords:PACS 73.20.At  75.50.Xx  79.60.Fr
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