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Spin Transition in Iron Compounds

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Book cover Chemical Mössbauer Spectroscopy

Abstract

First-row transition metal complexes with d4 up to d7 electron configuration in octahedral ligand fields (and d8 electron configuration in six-coordinate complexes of lower symmetry) may undergo temperature dependent high spin (HS) ⇌ low spin (LS) transition, provided the ligand field strength (Δ), including low symmetry contributions, becomes comparable in magnitude with the mean spin pairing energy (P). At a critical field strength Δcrit = P, the energy levels of the two spin states cross. This is illustrated in Fig. 1, where a simplified Tanabe-Sugano type energy level diagram for d6 systems (e.g. Fe2+, Co3+) is shown as an example. For weak ligand fields, Δ < Δcrit., the HS state 5T2g(Oh) is the ground state; for strong ligand fields, Δ >Δcrit, the LS state1A1g(Oh) becomes more stable. If the difference ∣Δ-P∣, or, in terms of thermodynamics, the difference in Gibbs free energy ΔG=G(HS)-G(LS), is on the order of thermal energy kT, both spin states HS and LS may be populated in thermal equilibrium.

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References

  1. L. Cambi, A. Cagnasso, Atti Accad. Naz. Lincei 13, 809 (1931)

    CAS  Google Scholar 

  2. L. Cambi, L. Szegö, Ber. dtsch. chem. Ges. 64, 259 (1931).

    Google Scholar 

  3. R.H. Martin, A.H. White, Transition Metal Chemistry, 4, 113 (1968).

    CAS  Google Scholar 

  4. L. Sacconi, Pure Appl. Chem. 27, 161 (1971).

    Article  CAS  Google Scholar 

  5. H.A. Goodwin, Coord. Chem. Rev. 18, 293 (1976).

    Article  CAS  Google Scholar 

  6. P. Gütlich, Struct. Bonding44, 83 (1981).

    Article  Google Scholar 

  7. P.G. Sim, E. Sinn, J. Am. Chem. Soc. 103, 241 (1981).

    Article  CAS  Google Scholar 

  8. J.H. Ammeter, L. Zoller, J. Bachmann, E. Baltzer, E. Gamp, R. Bucher, E. Deiss, Helv. Chim. Acta64, 1063 (1981).

    Article  CAS  Google Scholar 

  9. W. Kläui, J. Chem. Soc. Chem. Commun. 700 (1979).

    Google Scholar 

  10. P. Gütlich, B.R. McGarvey, W. Kläui, Inorg. Chem. 19,3704 (1980).

    Article  Google Scholar 

  11. M. Eibschütz, M. Lines, F.J. DiSalvo, Phys. Rev. B15, 103 (1977).

    Google Scholar 

  12. S. Ramasesha, T.V. Ramakrishnan, C.N.R. Rao, J. Phys. C. 12, 1307 (1979).

    Article  CAS  Google Scholar 

  13. H. Imoto, A. Simon, Inorg. Chem. 21308 (1982).

    Article  CAS  Google Scholar 

  14. C.J. Ballhausen, Introduction to Ligand Field Theory, McGraw-Hill, New York 1962.

    Google Scholar 

  15. M.F. Tweedle, L.J. Wilson, J. Am. Chem. Soc. 98, 4824 (1976).

    Article  CAS  Google Scholar 

  16. Y. Maeda, N. Tsutsumi, Y.Takashima, Chem. Phys. Lett. 88, 248 (1982).

    Article  CAS  Google Scholar 

  17. W.D. Federer, D.N. Hendrickson, private communication.

    Google Scholar 

  18. M. Sorai, S. Seki, J. Phys. Chem. Solids35, 555 (1974).

    Article  CAS  Google Scholar 

  19. W.A. Baker, H.M. Bobonich, Inorg. Chem. 3, 1184 (1964).

    Article  CAS  Google Scholar 

  20. E.W. Müller, P. Gütlich, unpublished measurements.

    Google Scholar 

  21. M. Cox, J. Darken, B.W. Fitzsimmons, A.W. Smith, L. Larkworthy, K. Rogers, J.C.S. Chem. Comm. 105, 1970.

    Google Scholar 

  22. G.W. Flynn, N. Sutin, in: Chemical and Biochemical Applications of Lasers, Vol. 1 (C.B. Moore, ed.), Academic Press New York 1974.

    Google Scholar 

  23. E.V. Dose, M.A. Hoselton, N. Sutin, M.F. Tweedle, L.J. Wilson, J. Am. Chem. Soc. 100, 1141 (1978)

    Article  CAS  Google Scholar 

  24. J.K. Beattie, R.A. Binstead, R.J. West, J. Am. Chem. Soc. 100, 3044 (1978).

    Article  CAS  Google Scholar 

  25. N. Sutin, Acc. Chem. Res. 15, 275 (1982).

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

  27. A.T. Casey, F. Isaac, Aust. J. Chem. 20, 2765 (1967).

    Article  CAS  Google Scholar 

  28. P. Ganguli, P. Gütlich, E.W. Müller, W. Irler, J.C.S. Dalton 441 (1981).

    Google Scholar 

  29. E.W. Müller, H. Spiering, P. Gütlich, Chem. Phys. Lett. 93, 567 (1982).

    Article  Google Scholar 

  30. E.W. Müller, H.Spiering, P. Gütlich, J. Chem. Phys. 79, 1439 (1983).

    Article  Google Scholar 

  31. M.S. Haddad, W.D. Federer, M.W. Lynch, D.N. Hendrickson, J. Am. Chem. Soc. 102, 1468 (1980);Inorg. Chem. 20, 123 (1981); ibid. p. 131.

    Article  CAS  Google Scholar 

  32. E.W. Müller, Dissertation, University of Mainz, Chemistry Dept. 1982.

    Google Scholar 

  33. C.N.R. Rao, K.J. Rao, “Phase Transitions in Solids”, McGraw-Hill, New York 1978.

    Google Scholar 

  34. K. Madeja, W. Wilke, and S. Schmidt, Z. anorg. Chem. 346, 306 (1966).

    Article  CAS  Google Scholar 

  35. M. Mikami, M. Konno, Y. Saito, Chem. Phys. Lett. 63, 566 (1979).

    Article  CAS  Google Scholar 

  36. R.D. Shannon, C.T. Prewitt, Acta Crystallogr. B26, 1076 (1970).

    Google Scholar 

  37. Y. Qi, E.W. Müller, H. Spiering, P. Gütlich, Chem. Phys. Lett. 101, 503 (1983).

    Article  CAS  Google Scholar 

  38. G.A. Renovitch, W.A. Baker Jr., J. Am. Chem. Soc. 89, 6377 1967

    Article  CAS  Google Scholar 

  39. H. Spiering, E. Meissner, H. Köppen, E.W. Miiller, P. Gütlich, Chem. Phys. 68, 65 (1982).

    Article  CAS  Google Scholar 

  40. H. Köppen, E.W. Müller, C.P. Köhler, H. Spiering, E. Meissner, P. Gütlich, Chem. Phys. Lett. 91, 348 (1982).

    Article  Google Scholar 

  41. C.P. Köhler, in partial fulfilment of the doctoral thesis, University of Mainz, Chemistry Dept., 1984.

    Google Scholar 

  42. E. König, Ber. Bunsengesellsch. phys. Chem. 76, 975 (1972).

    Google Scholar 

  43. E. König, G. Ritter, H.A. Goodwin, Chem. Phys. 1, 17 (1973).

    Article  Google Scholar 

  44. E. König, G. Ritter, H.A. Goodwin, Chem. Phys. 5, 211 (1974).

    Article  Google Scholar 

  45. E. König, G. Ritter, W. Irler, H.A. Goodwin, B. Kanellakopulos, J. Phys. Chem. Solids39, 521 (1978).

    Article  Google Scholar 

  46. E. Konig, G. Ritter, W. Irler, S.M. Nelson, Inorg. Chim. Acta37, 169 (1979).

    Article  Google Scholar 

  47. H. Köppen, in partial fulfilment of his doctoral thesis, University of Mainz, Chemistry Dept., 1984.

    Google Scholar 

  48. D.M.L. Goodgame, A.A.S.C. Machado, Inorg. Chem. 6, 2031 (1969).

    Article  Google Scholar 

  49. M.A. Hoselton, L.J. Wilson, R.S. Drago, J. Am. Chem. Soc. 97, 1722 (1975).

    Article  CAS  Google Scholar 

  50. P. Gütlich, H. Köppen, R. Link, H.G. Steinhäuser, J. Chem.Phys. 70, 3977 (1979).

    Article  Google Scholar 

  51. B.A. Katz, C.E. Strouse, J. Am. Chem. Soc. 101, 6214 (1979).

    Article  CAS  Google Scholar 

  52. A.M. Greenaway, C.J. O’Connor, A. Schrock, E. Sinn, Inorg. Chem. 18, 2692 (1979).

    Article  CAS  Google Scholar 

  53. A.M. Greenaway, E. Sinn, J. Am. Chem, Soc. 100, 8080 (1978).

    Article  CAS  Google Scholar 

  54. M. Sorai, J. Ensling, K.M. Hasselbach, P. Gütlich, Chem. Phys. 20, 951 (1977).

    Article  Google Scholar 

  55. I. Sanner, E. Meissner, H. Köppen, H. Spiering, P. Gütlich, Chem. Phys. (1984), in press.

    Google Scholar 

  56. E. Meissner, H. Köppen, H. Spiering, P. Gütlich, Chem. Phys. Lett. 95, 163 (1983).

    Article  CAS  Google Scholar 

  57. L. Wiehl, C.P. Köhler, P. Gutlich, to be published.

    Google Scholar 

  58. P. Gutlich, H. Koppen, H.G. Steinhauser, Chem. Phys. Lett. 74, 475 (1980).

    Article  Google Scholar 

  59. M. Sorai, J. Ensling, P. Gütlich, Chem. Phys. 18, 199 (1976).

    Article  CAS  Google Scholar 

  60. P. Gütlich, R. Link, H.G. Steinhäuser, Inorg. Chem. 17, 2509 (1978).

    Article  Google Scholar 

  61. P. Adler, H. Spiering, P. Gütlich, to be published.

    Google Scholar 

  62. D.B. Chesnut, J. Chem. Phys. 40, 405 (1964).

    Article  CAS  Google Scholar 

  63. J. Wajnflasz, Phys. stat. sol. 40, 537 (1970).

    Article  CAS  Google Scholar 

  64. R.A. Bari, J. Sivardiére, Phys. Rev. B5, 4466 (1972).

    Google Scholar 

  65. C.P. Slichter, H.G. Drickamer, J. Chem. Phys. 56, 2142 (1972).

    Article  CAS  Google Scholar 

  66. R. Zimmermann, E. König, J. Phys. Chem. Solids 38, 779 (1977).

    Article  CAS  Google Scholar 

  67. T. Kambara, J. Chem. Phys. 70, 4199 (1979).

    Article  CAS  Google Scholar 

  68. T. Kambara, J. Phys. Soc. Japan49, 1806 (1980).

    Article  CAS  Google Scholar 

  69. S. Ramasesha, T.V. Ramakrishnan, C.N.R. Rao, J. Phys. C (Sol. State Phys.)12, 1307 (1979).

    Article  CAS  Google Scholar 

  70. S. Ohnishi, S. Sugano, J. Phys. C (Sol. State Phys.)14, 39 (1981).

    Article  CAS  Google Scholar 

  71. J.D. Eshelby, Sol. State Phys. 3, 79 (1956).

    Article  CAS  Google Scholar 

  72. R. Zimmermann, H. Spiering, Phys. Stat. Sol. B67, 487 (1975).

    Google Scholar 

  73. J.H. Takemoto, B. Hutchinson, Inorg. Chem. 12, 705 (1973).

    Article  CAS  Google Scholar 

  74. H.G. Drickamer, C.W. Frank: Electronic Transitions and the High Pressure Chemistry and Physics of Solids, Chapman and Hall, London 1973.

    Google Scholar 

  75. J.R. Ferraro, J. Takemoto, Appl. Spectroscopy28, 66 (1974).

    Article  Google Scholar 

  76. G.J. Long, L.W. Becker, B.B. Hutchinson, in: “Mossbauer Spectroscopy and its Chemical Applications” (J.G.Stevens, G.K. Shenoy, eds.) Adv. Chem. Series, Am. Chem. Soc., Washington, D.C. 1981, p. 453.

    Google Scholar 

  77. E. Meissner, in partial fulfilment of the doctoral thesis, University of Mainz, Physics Department, 1984.

    Google Scholar 

  78. P.L. Franke, J.G. Haasnoot, A.P. Zuur, Inorg. Chim. Acta59, 5 (1982).

    Article  CAS  Google Scholar 

  79. E.W. Müller, J.Ensling, H. Spiering, P. Gutlich, Inorg. Chem. 22, 2074 (1983).

    Article  Google Scholar 

  80. S. Decurtins, P.Gütlich, C.P. Köhler, H.Spiering, Chem. Phys. Lett. 105, 1(1984).

    Article  CAS  Google Scholar 

  81. S. Decurtins, P. Gütlich, A. Hauser, K.M. Hasselbach, H. Spiering, to be published in Inorg. Chem.

    Google Scholar 

  82. S. Decurtins, P. Gütlich, C.P. Köhler, H. Spiering, J. Am. Chem. Soc., submitted.

    Google Scholar 

  83. R. Grimm, P. Gütlich, E. Kankeleit, R. Link, J. Chem. Phys. 67, 5491 (1977).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Institut für Anorganische und Analytische Chemie, Johannes-Gutenberg-Universität, D-6500, Mainz, West Germany

    Philipp Gütlich

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  1. Philipp Gütlich
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  1. Rutgers University, New Brunswick, New Jersey, USA

    R. H. Herber

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© 1984 Plenum Press, New York

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Gütlich, P. (1984). Spin Transition in Iron Compounds. In: Herber, R.H. (eds) Chemical Mössbauer Spectroscopy. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-2431-7_2

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  • DOI: https://doi.org/10.1007/978-1-4613-2431-7_2

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4612-9479-5

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