ENDOR identification of a Rh+ centre in solution-grown NaCl

(Note: The full text of this document is currently only available in the PDF Version )

Henk Vrielinck, Freddy Callens, Marieta Zdravkova and Paul Matthys


Abstract

X-Irradiation at room temperature produces three stable rhodium-related centres in solution-grown NaCl doped with Rh3+. Two have earlier been identified as Rh2+-centred complexes. The third centre, which could only be observed with electron nuclear double resonance (ENDOR), appeared to have cubic symmetry. In the present work this centre is identified as a (RhCl6)5- complex, substituting for (NaCl6)5-. The central Rh+ ion has a 4 configuration, leading to a centre with effective spin S=1. This is confirmed experimentally by the occurrence of a ΔMS=2 transition in the EPR spectrum. Interactions of the unpaired electrons with the central Rh nucleus, the first-shell CI and the fourth-shell Na nuclei are observed in the ENDOR spectrum. The angular dependence of these interactions shows that the centre has cubic symmetry. The spin Hamiltonian parameters obtained are used to estimate the crystal field splitting and the unpaired spin density over the complex.


References

  1. H. Vercammen, T. Ceulemans, D. Schoemaker, P. Moens and D. Vandenbroucke, Proceedings of the Imaging Science and Technology 49th Annual Conference, Minneapolis, 19–24 May 1996. The Society of Imaging Science and Technology, Springfield, Virginia, 1996, p. 54 Search PubMed.
  2. P. Moens, H. Vercammen, D. Vandenbroucke, F. Callens and D. Schoemaker, ref. 1, p. 56.
  3. R. S. Eachus and R. E. Graves, J. Chem. Phys., 1973, 59, 2160 CAS.
  4. R. S. Eachus and R. E. Graves, J. Chem. Phys., 1974, 61, 2860 CAS.
  5. J. R. Shock and M. T. Rogers, J. Chem. Phys., 1974, 62, 2640 CrossRef CAS.
  6. M. T. Olm, J. R. Niklas, J. M. Spaeth and M. C. R. Symons, Phys. Rev. B, 1974, 38, 4343 CrossRef CAS.
  7. S. Schweizer and J. M. Spaeth, J. Phys. Chem. Solids, 1997, 58, 859 CrossRef CAS.
  8. K. Sabbe, F. Callens and E. Boesman, Appl. Magn. Reson., submitted Search PubMed.
  9. N. M. Pinhal and N. V. Vugman, J. Phys. C, 1985, 18, 6273 CrossRef CAS.
  10. M. Zdravkova, H. Vrielinck, F. Callens, E. Boesman, H. Vercammen and D. Schoemaker, J. Appl. Phys., 1997, 82, 2476 CrossRef CAS.
  11. F. Callens, H. Vrielinck, P. Matthys, M. Zdravkova, H. Vercammen and D. Schoemaker, J. Appl. Phys., in press Search PubMed.
  12. H. Vercammen, D. Schoemaker, H. Käss, E. Goovaerts, A. Bouwen, H. Vrielinck and F. Callens, J. Appl. Phys., in press Search PubMed.
  13. J. S. Griffith, The Theory of Transition-Metal Ions, Cambridge University Press, 1961 Search PubMed.
  14. J. W. Orton, P. Auzins and J. E. Wertz, Phys. Rev., 1960, 119, 1691 CrossRef CAS.
  15. J. W. Orton, P. Auzins, J. H. E. Griffiths and J. E. Wertz, Proc. Phys. Soc., 1961, 78, 554 Search PubMed.
  16. A. Abragam and B. Bleaney, Electron Paramagnetic Resonance of Transition Ions, Clarendon Press, Oxford, 1970 Search PubMed.
Click here to see how this site uses Cookies. View our privacy policy here.