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Lattice phonon modes of the spin crossover crystal [Fe(phen)2(NCS)2] studied by THz, IR, Raman spectroscopies and DFT calculations

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Abstract

[Fe(phen)2(NCS)2] is a prototype transition metal complex material that undergoes a phase transition between low-spin (LS) and high-spin (HS) phases, induced by temperature, pressure or light. Vibrational modes play a key role for spin-state switching both in thermal and photoinduced cases, by contributing to vibrational entropy for thermal equilibrium transitions or driving the fast structural trapping of the photoinduced high-spin state. Here we study the crystal phonon modes of [Fe(phen)2(NCS)2] by combining THz, IR, and Raman spectroscopies sensitive to modes in different frequency ranges and symmetries. We compare the experimental results with DFT calculations performed in a periodic 3D crystal for understanding the phonon modes in the crystal. Indeed, each vibrational mode of the isolated molecule combines into several modes of different symmetries and frequencies in the crystal, as the unit cell contains four molecules. We focus our attention on the HS symmetric and anti-symmetric breathing modes in the crystal as well as on the N-CS stretching modes.

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Authors and Affiliations

  1. Univ Rennes, CNRS, IPR (Institut de Physique de Rennes) - UMR 6251, 35000, Rennes, France

    Eric Collet, Giovanni Azzolina, Laurent Guerin, Roman Bertoni, Alain Moréac & Marco Cammarata

  2. Department of Physics, Graduate School of Science, Kyoto University, Kitashirakawa-oiwakecho, Sakyo-ku, Kyoto, 606-8502, Japan

    Tomoaki Ichii & Koichiro Tanaka

  3. CNRS, University of Bordeaux, ICMCB, UMR 5026, 87 Avenue du Docteur-Albert-Schweitzer, 33608, Pessac, France

    Nathalie Daro, Guillaume Chastanet & Samir F. Matar

  4. Faculty of Physics, Adam Mickiewicz University in Poznan, Umultowska 85, 61-614, Poznan, Poland

    Jacek Kubicki

  5. Lebanese German University (LGU), Sahel Alma Campus, PO Box 206, Jounieh, Lebanon

    Samir F. Matar

Authors
  1. Eric Collet
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  2. Giovanni Azzolina
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Correspondence to Eric Collet.

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Supplementary material in the form of one zip file available from the Journal web page at https://doi.org/10.1140/epjb/e2018-90553-2

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Collet, E., Azzolina, G., Ichii, T. et al. Lattice phonon modes of the spin crossover crystal [Fe(phen)2(NCS)2] studied by THz, IR, Raman spectroscopies and DFT calculations. Eur. Phys. J. B 92, 12 (2019). https://doi.org/10.1140/epjb/e2018-90553-2

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  • DOI: https://doi.org/10.1140/epjb/e2018-90553-2

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