Physics and Chemistry of Minerals

, Volume 41, Issue 5, pp 347–359 | Cite as

Theoretical study of the local charge compensation and spectroscopic properties of B-type carbonate defects in apatite

  • Haohao Yi
  • Etienne Balan
  • Christel Gervais
  • Loïc Ségalen
  • Marc Blanchard
  • Michele Lazzeri
Original Paper
First Online:
Received:
Accepted:

Abstract

The structure and spectroscopic properties of selected models of B-type carbonate defects in apatite locally compensated by fluoride or hydroxyl ions are investigated using first-principles quantum mechanical calculations. Theoretical infrared absorption spectra and 13C, and 19F nuclear magnetic resonance chemical shifts are determined. Among the investigated models, only the clumped (CO3 2−, F−) defect, with the carbonate group close to the sloping face of the tetrahedral site and the F− ion at the remaining apex, corresponds to previous experimental observations performed on carbonate-fluorapatite samples. Although the substitution of hydroxyl by fluoride ions is commonly observed in minerals, the clumped (CO3 2−, OH−) defects are unlikely to occur in apatite, considering both their theoretical spectroscopic properties and relative stability. Anionic F− for OH− exchange between channel and B sites displays a preference of ~20 kJ/mol for the local charge compensation by fluoride ions at the B-site, pointing to a significantly different behavior of F− and OH− ions in the charge compensation mechanism. This difference is ascribed to the poor H-bond acceptor character of available oxygen atoms surrounding the apex of the tetrahedral site. The explicit calculation of the infrared absorption spectra of the defect models is also used to interpret the significant difference observed in the linewidth of the ν2 and ν3 CO3 infrared powder absorption bands of carbonated apatite samples. It is shown that for a concentration of 4.4 wt% of CO2, long-range electrostatic effects already significantly contribute to the broadening of the ν3 CO3 bands in apatite.

Keywords

Apatite Carbonate substitution First-principles DFT FTIR NMR 
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Notes

Acknowledgments

This work was performed using HPC resources from GENCI-IDRIS (Grants 041519 and 091461). Funding by the UPMC Emergence program and the CNRS-INSU “INTERRVIE” program is acknowledged. This is a contribution of LabEx MATISSE.

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Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Haohao Yi
    • 1
    • 2
    • 3
  • Etienne Balan
    • 1
    • 2
    • 3
  • Christel Gervais
    • 4
    • 5
    • 6
  • Loïc Ségalen
    • 7
    • 8
  • Marc Blanchard
    • 1
    • 2
    • 3
  • Michele Lazzeri
    • 1
    • 2
    • 3
  1. 1.Sorbonne Universités, UPMC Univ Paris 06, UMR 7590, IMPMCParisFrance
  2. 2.CNRS, UMR 7590IMPMCParisFrance
  3. 3.IRD, UMR 206IMPMCParisFrance
  4. 4.Sorbonne Universités, UPMC Univ Paris 06, UMR 7574, Chimie de la Matière Condensée de ParisParisFrance
  5. 5.CNRS, UMR 7574Chimie de la Matière Condensée de ParisParisFrance
  6. 6.Collège de France, UMR 7574Chimie de la Matière Condensée de ParisParisFrance
  7. 7.Sorbonne Universités, UPMC Univ Paris 06, UMR 7193, ISTEP, Biominéralisations et Environnements SédimentairesParisFrance
  8. 8.CNRS, UMR 7193ISTEPParisFrance

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