Skip to main content
SpringerLink
Log in

EPR of V4+ and Fe3+ in titanites

  • Published:
Physics and Chemistry of Minerals Aims and scope Submit manuscript

Abstract

EPR investigations of yellow-green titanites from four localities showed presence of V4+ and Fe3+. They were investigated at X-band and room temperature. For V4+ the principal values of the g matrix and 51V hyperfine splitting and the directions of their principal axes indicate presence of a VO2+ ion substituting for Ti. Due to a high zero-field splitting only approximate values of the fine structure parameters of Fe3+ could be determined. With directions of their principal axes very similar to those of V4+ this ion must also substitute for Ti. Unusually large linewidths for both ions with little variation for samples from different localities are ascribed to the reported domain structure of titanites and accumulation of impurities in the domain boundaries. While for Fe3+ a small variation of the fine structure parameters explains this broadening, for V4+ a distribution of g-factors equal to its total anisotropy must be responsible whereas the V=0 bond length is remarkably constant. Due to preferential incorporation of impurities in the grain boundaries a contribution of dipolar broadening cannot be excluded.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Assa RS (1970) Powder lineshape in the electron paramagnetic resonance spectra of high-spin ferric complexes. J Chem Phys 52:3919–3930

    Google Scholar 

  • Ball D, Wanklyn BM (1976) Coloured synthetic zircon crystals. Phys Status Solidi A 36:307–316

    Google Scholar 

  • Ballutaud D, Bordes E, Courtine P (1982) An E.S.R. study of paramagnetic centers in α-VOPO4 and α-VOPO4·2H2O. Mat Res Bull 17:519–526

    Google Scholar 

  • Chand P, Jain VK, Upreti GC (1988) EPR of VO2+ molecular ion. Magn Reson Rev (to be published)

  • Cerný P, Riva di Sanseverino L (1972) Comments on crystal chemistry of titanite. Neues Jahrb Mineral Mh 97–103

  • Dowsing RD, Gibson JP (1969) Electron spin resonance of high-spin d5 systems. J Chem Phys 50:294–303

    Google Scholar 

  • Havlićek V, Novák P (1974) EPR linewidth and intensity of V4+ ion in NaCa2Mg2V3O12 garnet. Czech J Phys B 24:198–202

    Google Scholar 

  • Heming M, Lehmann G (1987) Superposition model for the zero-field splittings of 3d-ion EPR: Experimental tests, theoretical calculations and applications. In: Weil JA (ed) Electronic magnetic resonance of the solid state. The Canadian Society for Chemistry, Ottawa, pp 163–174

    Google Scholar 

  • Higgins JB, Ribbe PH (1976) The crystal chemistry and space groups of natural and synthetic titanites. Am Mineral 61:878–888

    Google Scholar 

  • Jordan B, Calvo C (1973) Crystal structure of α-VPO5. Can J Chem 51:2621–2626

    Google Scholar 

  • Marfunin AS, Bershov LS, Mineeva RM (1966) La résonance paramagnétique électronique de l'ion VO2+ dans le sphène et l'apophyllite et de l'ion Mn2+ dans la tremolite, l'apophyllite et la scheelite. Bull Soc Fr Mineral Cristallogr 89:177–183

    Google Scholar 

  • Mongiorgi R, Riva di Sanseverino L (1968) A reconsideration of the structure of titanite CaTiOSiO4. Mineral Petrogr Acta 14:123–141

    Google Scholar 

  • Nienhaus K, Stegger P, Lehmann G, Schneider JR (1986) Assessment of quality of quartz crystals by EPR and γ-ray diffraction. J Cryst Growth 74:320–327

    Google Scholar 

  • Rockenbauer A, Simon P (1975) Linewidth variations of EPR spectra in solid state. J Magn Reson 18:320–327

    Google Scholar 

  • Sahama TG (1946) On the chemistry of the mineral titanite. C R Soc Géol Finlande 19:88–120

    Google Scholar 

  • Schmitz B, Jakubith M, Lehmann G (1979) A simple and convenient EPR standard for determination of g-factors and spin concentrations. Z Naturforsch 34a:906–908

    Google Scholar 

  • Speer A, Gibbs GV (1976) The crystal structure of synthetic titanite, CaTiOSiO4, and the domain textures of natural titanites. Am Mineral 61:238–247

    Google Scholar 

  • Taborsky FK (1976) Die Geochemie der Titanite. Habilitationsschrift, Freiburg, p 36

    Google Scholar 

  • Tachez M, Theobald F (1980) Liaisons hydrogène dans les cristaux de sulfate de vanadyle trihydrate (VOSO4·3H2O). Comparison structurale de quatre sulfates de vanadyle hydratés. Acta Crystallogr B 36:2873–2880

    Google Scholar 

  • Vassilikou-Dova AB, Lehmann G (1988) EPR of V4+ in apophyllite. Phys Status Solidi B (submitted)

  • Zachariasen WH (1930) The crystal structure of titanite. Z Kristallogr 73:7–16

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institut für Physikalische Chemie, Westfälische Wilhelms-Universität, Schloßplatz 4, D-4400, Münster, West Germany

    A. B. Vassilikou-Dova & G. Lehmann

Authors
  1. A. B. Vassilikou-Dova
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. G. Lehmann
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Permanent address: University of Athens, Department of Physics, Solid State Section, 104, Solonos Street, 106 80 Athens, Greece

Rights and permissions

Reprints and permissions

About this article

Cite this article

Vassilikou-Dova, A.B., Lehmann, G. EPR of V4+ and Fe3+ in titanites. Phys Chem Minerals 15, 559–563 (1988). https://doi.org/10.1007/BF00311026

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00311026

Keywords

Search

Navigation