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

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.

Graphical abstract

This is a preview of subscription content, log in to check access.

References

  1. 1.

    M.A. Halcrow, Spin-Crossover Materials: Properties and Applications (John Wiley & Sons, Inc., 2013)

  2. 2.

    R. Bertoni, M. Lorenc, T. Graber, R. Henning, K. Moffat, J.F. Létard, E. Collet, Crystengcomm 18, 7269 (2016)

    Article  Google 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)

    Article  Google 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)

    ADS  Article  Google 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)

    Article  Google Scholar 

  6. 6.

    M.L. Boillot, J. Zarembowitch, J.P. Itie, A. Polian, E. Bourdet, J.G. Haasnoot, New J. Chem. 26, 313 (2002)

    Article  Google 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)

    Article  Google 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)

    Article  Google Scholar 

  9. 9.

    V. Briois, C.C.D. Moulin, P. Sainctavit, C. Brouder, A.M. Flank, J. Am. Chem. Soc. 117, 1019 (1995)

    Article  Google Scholar 

  10. 10.

    A. Tissot, C. Enachescu, M.-L. Boillot, J. Mater. Chem. 22, 20451 (2012)

    Article  Google Scholar 

  11. 11.

    C. Balde, C. Desplanches, A. Wattiaux, P. Guionneau, P. Gutlich, J.F. Letard, Dalton Trans. 20, 2702 (2008)

    Article  Google Scholar 

  12. 12.

    E. Koenig, K. Madeja, Inorg. Chem. 6, 48 (1967)

    Article  Google Scholar 

  13. 13.

    G. Baranovic, D. Babic, Spectrochim. Acta A 60, 1013 (2004)

    ADS  Article  Google Scholar 

  14. 14.

    V. Briois, P. Sainctavit, G.J. Long, F. Grandjean, Inorg. Chem. 40, 912 (2001)

    Article  Google Scholar 

  15. 15.

    S. Bonhommeau, G. Molnár, M. Goiran, K. Boukheddaden, A. Bousseksou, Phys. Rev. B 74, 064424 (2006)

    ADS  Article  Google 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)

    ADS  Article  Google 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)

    Article  Google Scholar 

  18. 18.

    J.A. Real, B. Gallois, T. Granier, F. Suez-Panama, J. Zarembowitch, Inorg. Chem. 31, 4972 (1992)

    Article  Google Scholar 

  19. 19.

    E. Collet, P. Guionneau, C. R. Chim. 21, 1133 (2018)

    Article  Google 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)

    ADS  Article  Google 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)

    Article  Google Scholar 

  23. 23.

    A. Metatla, H. Latelli, W. Nicolazzi, A. Bousseksou, Eur. Phys. J. B 85, 205 (2012)

    ADS  Article  Google Scholar 

  24. 24.

    M. Sorai, S. Seki, J. Phys. Chem. Solids 35, 555 (1974)

    ADS  Article  Google Scholar 

  25. 25.

    J.H. Takemoto, B. Streusan, B. Hutchins, Spectrochim. Acta A 30, 827 (1974)

    ADS  Article  Google 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)

    ADS  Article  Google 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)

    Article  Google Scholar 

  28. 28.

    M. Chergui, E. Collet, Chem. Rev. 117, 11025 (2017)

    Article  Google 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)

    Article  Google 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)

    ADS  Article  Google Scholar 

  31. 31.

    A. Subedi, A. Cavalleri, A. Georges, Phys. Rev. B 89, 220301 (2014)

    ADS  Article  Google Scholar 

  32. 32.

    M. Forst, C. Manzoni, S. Kaiser, Y. Tomioka, Y. Tokura, R. Merlin, A. Cavalleri, Nat. Phys. 7, 854 (2011)

    Article  Google Scholar 

  33. 33.

    J. Dai, N. Karpowicz, X.C. Zhang, Phys. Rev. Lett. 103, 023001 (2009)

    ADS  Article  Google Scholar 

  34. 34.

    J. Dai, X. Xie, X.C. Zhang, Phys. Rev. Lett. 97, 103903 (2006)

    ADS  Article  Google Scholar 

  35. 35.

    G. Kresse, J. Furthmüller, Phys. Rev. B 54, 11169 (1996)

    ADS  Article  Google Scholar 

  36. 36.

    P. Hohenberg, W. Kohn, Phys. Rev. 136, B864 (1964)

    ADS  Article  Google Scholar 

  37. 37.

    G. Kresse, D. Joubert, Phys. Rev. B 59, 1758 (1999)

    ADS  Article  Google Scholar 

  38. 38.

    J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996)

    ADS  Article  Google 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)

  40. 40.

    S.F. Matar, P. Guionneau, G. Chastanet, Int. J. Mol. Sci. 16, 4007 (2015)

    Article  Google Scholar 

  41. 41.

    M. Reiher, Inorg. Chem. 41, 6928 (2002)

    Article  Google 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)

    Article  Google Scholar 

Download references

Author information

Affiliations

Authors

Corresponding author

Correspondence to Eric Collet.

Additional information

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

Electronic supplementary material

Supplementary data

ZIP file

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

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

Download citation

Keywords

  • Solid State and Materials