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

  • Eric ColletEmail author
  • Giovanni Azzolina
  • Tomoaki Ichii
  • Laurent Guerin
  • Roman Bertoni
  • Alain Moréac
  • Marco Cammarata
  • Nathalie Daro
  • Guillaume Chastanet
  • Jacek Kubicki
  • Koichiro Tanaka
  • Samir F. Matar
Regular Article


[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.

Graphical abstract


Solid State and Materials 

Supplementary material


  1. 1.
    M.A. Halcrow, Spin-Crossover Materials: Properties and Applications (John Wiley & Sons, Inc., 2013) Google Scholar
  2. 2.
    R. Bertoni, M. Lorenc, T. Graber, R. Henning, K. Moffat, J.F. Létard, E. Collet, Crystengcomm 18, 7269 (2016) CrossRefGoogle Scholar
  3. 3.
    R. Bertoni, M. Cammarata, M. Lorenc, S.F. Matar, J.F. Letard, H.T. Lemke, E. Collet, Acc. Chem. Res. 48, 774 (2015) CrossRefGoogle Scholar
  4. 4.
    M. Cammarata, R. Bertoni, M. Lorenc, H. Cailleau, S. Di Matteo, C. Mauriac, S.F. Matar, H. Lemke, M. Chollet, S. Ravy, C. Laulhe, J.F. Letard, E. Collet, Phys. Rev. Lett. 113, 227402 (2014) ADSCrossRefGoogle Scholar
  5. 5.
    K.L. Ronayne, H. Paulsen, A. Hofer, A.C. Dennis, J.A. Wolny, A.I. Chumakov, V. Schunemann, H. Winkler, H. Spiering, A. Bousseksou, P. Gutlich, A.X. Trautwein, J.J. McGarvey, Phys. Chem. Chem. Phys. 8, 4685 (2006) CrossRefGoogle Scholar
  6. 6.
    M.L. Boillot, J. Zarembowitch, J.P. Itie, A. Polian, E. Bourdet, J.G. Haasnoot, New J. Chem. 26, 313 (2002) CrossRefGoogle Scholar
  7. 7.
    M. Marchivie, P. Guionneau, J.A.K. Howard, G. Chastanet, J.F. Letard, A.E. Goeta, D. Chasseau, J. Am. Chem. Soc. 124, 194 (2002) CrossRefGoogle Scholar
  8. 8.
    J.J. Lee, H.S. Sheu, C.R. Lee, J.M. Chen, J.F. Lee, C.C. Wang, C.H. Huang, Y. Wang, J. Am. Chem. Soc. 122, 5742 (2000) CrossRefGoogle Scholar
  9. 9.
    V. Briois, C.C.D. Moulin, P. Sainctavit, C. Brouder, A.M. Flank, J. Am. Chem. Soc. 117, 1019 (1995) CrossRefGoogle Scholar
  10. 10.
    A. Tissot, C. Enachescu, M.-L. Boillot, J. Mater. Chem. 22, 20451 (2012) CrossRefGoogle Scholar
  11. 11.
    C. Balde, C. Desplanches, A. Wattiaux, P. Guionneau, P. Gutlich, J.F. Letard, Dalton Trans. 20, 2702 (2008) CrossRefGoogle Scholar
  12. 12.
    E. Koenig, K. Madeja, Inorg. Chem. 6, 48 (1967) CrossRefGoogle Scholar
  13. 13.
    G. Baranovic, D. Babic, Spectrochim. Acta A 60, 1013 (2004) ADSCrossRefGoogle Scholar
  14. 14.
    V. Briois, P. Sainctavit, G.J. Long, F. Grandjean, Inorg. Chem. 40, 912 (2001) CrossRefGoogle Scholar
  15. 15.
    S. Bonhommeau, G. Molnár, M. Goiran, K. Boukheddaden, A. Bousseksou, Phys. Rev. B 74, 064424 (2006) ADSCrossRefGoogle Scholar
  16. 16.
    A. Rotaru, F. Varret, A. Gindulescu, J. Linares, A. Stancu, J.F. Letard, T. Forestier, C. Etrillard, Eur. Phys. J. B 84, 439 (2011) ADSCrossRefGoogle Scholar
  17. 17.
    J.F. Letard, P. Guionneau, L. Rabardel, J.A.K. Howard, A.E. Goeta, D. Chasseau, O. Kahn, Inorg. Chem. 37, 4432 (1998) CrossRefGoogle Scholar
  18. 18.
    J.A. Real, B. Gallois, T. Granier, F. Suez-Panama, J. Zarembowitch, Inorg. Chem. 31, 4972 (1992) CrossRefGoogle Scholar
  19. 19.
    E. Collet, P. Guionneau, C. R. Chim. 21, 1133 (2018) CrossRefGoogle Scholar
  20. 20.
    M. Buron-Le Cointe, J. Hébert, C. Baldé, N. Moisan, L. Toupet, P. Guionneau, J.F. Létard, E. Freysz, H. Cailleau, E. Collet, Phys. Rev. B 85, 064114 (2012) ADSCrossRefGoogle Scholar
  21. 21.
    J.P. Tuchagues, A. Bousseksou, G. Molnar, J.J. McGarvey, F. Varret, Top. Curr. Chem. 235, 85 (2004) Google Scholar
  22. 22.
    G. Brehm, M. Reiher, S. Schneider, J. Phys. Chem. A 106, 12024 (2002) CrossRefGoogle Scholar
  23. 23.
    A. Metatla, H. Latelli, W. Nicolazzi, A. Bousseksou, Eur. Phys. J. B 85, 205 (2012) ADSCrossRefGoogle Scholar
  24. 24.
    M. Sorai, S. Seki, J. Phys. Chem. Solids 35, 555 (1974) ADSCrossRefGoogle Scholar
  25. 25.
    J.H. Takemoto, B. Streusan, B. Hutchins, Spectrochim. Acta A 30, 827 (1974) ADSCrossRefGoogle Scholar
  26. 26.
    H.T. Lemke, K.S. Kjaer, R. Hartsock, T. Brandt van Driel, M. Chollet, J.M. Glownia, S. Song, D. Zhu, E. Pace, S.F. Matar, M.N. Nielsen, M. Benfatto, K.J. Gaffney, E. Collet, M. Cammarata, Nat. Commun. 8, 15342 (2017) ADSCrossRefGoogle Scholar
  27. 27.
    S. Zerdane, L. Wilbraham, M. Cammarata, O. Lasco, E. Rivière, M.L. Boillot, I. Ciofini, E. Collet, Chem. Sci. 8, 4978 (2017) CrossRefGoogle Scholar
  28. 28.
    M. Chergui, E. Collet, Chem. Rev. 117, 11025 (2017) CrossRefGoogle Scholar
  29. 29.
    A. Marino, M. Cammarata, S.F. Matar, J.-F. Létard, G. Chastanet, M. Chollet, J.M. Glownia, H.T. Lemke, E. Collet, Struct. Dyn. 3, 023605 (2016) CrossRefGoogle Scholar
  30. 30.
    R. Bertoni, M. Lorenc, H. Cailleau, A. Tissot, J. Laisney, M.L. Boillot, L. Stoleriu, A. Stancu, C. Enachescu, E. Collet, Nat. Mater. 15, 606 (2016) ADSCrossRefGoogle Scholar
  31. 31.
    A. Subedi, A. Cavalleri, A. Georges, Phys. Rev. B 89, 220301 (2014) ADSCrossRefGoogle Scholar
  32. 32.
    M. Forst, C. Manzoni, S. Kaiser, Y. Tomioka, Y. Tokura, R. Merlin, A. Cavalleri, Nat. Phys. 7, 854 (2011) CrossRefGoogle Scholar
  33. 33.
    J. Dai, N. Karpowicz, X.C. Zhang, Phys. Rev. Lett. 103, 023001 (2009) ADSCrossRefGoogle Scholar
  34. 34.
    J. Dai, X. Xie, X.C. Zhang, Phys. Rev. Lett. 97, 103903 (2006) ADSCrossRefGoogle Scholar
  35. 35.
    G. Kresse, J. Furthmüller, Phys. Rev. B 54, 11169 (1996) ADSCrossRefGoogle Scholar
  36. 36.
    P. Hohenberg, W. Kohn, Phys. Rev. 136, B864 (1964) ADSCrossRefGoogle Scholar
  37. 37.
    G. Kresse, D. Joubert, Phys. Rev. B 59, 1758 (1999) ADSCrossRefGoogle Scholar
  38. 38.
    J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996) ADSCrossRefGoogle Scholar
  39. 39.
    M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, G.A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. Marenich, J. Bloino, B.G. Janesko, R. Gomperts, B. Mennucci, H.P. Hratchian, J.V. Ortiz, A.F. Izmaylov, J.L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V.G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J.A. Montgomery, Jr. J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, J.M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R.L. Martin, K. Morokuma, O. Farkas, J.B. Foresman, D.J. Fox, Gaussian 09, Revision A.02 (Gaussian, Inc., Wallingford CT, 2016) Google Scholar
  40. 40.
    S.F. Matar, P. Guionneau, G. Chastanet, Int. J. Mol. Sci. 16, 4007 (2015) CrossRefGoogle Scholar
  41. 41.
    M. Reiher, Inorg. Chem. 41, 6928 (2002) CrossRefGoogle Scholar
  42. 42.
    R. Bertoni, M. Lorenc, A. Tissot, M.L. Boillot, E. Collet, Coord. Chem. Rev. 66, 282 (2015) Google Scholar
  43. 43.
    M. Marchivie, P. Guionneau, J.F. Letard, D. Chasseau, Acta Crystallogr. B 61, 25 (2005) CrossRefGoogle Scholar

Copyright information

© EDP Sciences, SIF and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Eric Collet
    • 1
    Email author
  • Giovanni Azzolina
    • 1
  • Tomoaki Ichii
    • 2
  • Laurent Guerin
    • 1
  • Roman Bertoni
    • 1
  • Alain Moréac
    • 1
  • Marco Cammarata
    • 1
  • Nathalie Daro
    • 3
  • Guillaume Chastanet
    • 3
  • Jacek Kubicki
    • 4
  • Koichiro Tanaka
    • 2
  • Samir F. Matar
    • 3
    • 5
  1. 1.Univ Rennes, CNRS, IPR (Institut de Physique de Rennes) - UMR 6251RennesFrance
  2. 2.Department of PhysicsGraduate School of Science, Kyoto University, Kitashirakawa-oiwakechoSakyo-ku, KyotoJapan
  3. 3.CNRS, University of Bordeaux, ICMCB, UMR 5026PessacFrance
  4. 4.Faculty of Physics, Adam Mickiewicz University in PoznanPoznanPoland
  5. 5.Lebanese German University (LGU), Sahel Alma CampusJouniehLebanon

Personalised recommendations