Mechanism of Zn stabilization in hydroxyapatite and hydrated (0 0 1) surfaces of hydroxyapatite

M. Matos*, J. Terra, Donald E Ellis

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Scopus citations


A basic understanding of Zn incorporation on bulk and hydrated (001) surfaces of hydroxyapatite (HA) is attained through electronic structure calculations which use a combined first principles density functional (DFT) and extended Hückel tight binding (EHTB) methodology. A Zn substituted hydroxyapatite relaxed structure is obtained through a periodic cell DFT geometry optimization method. Electronic structure properties are calculated by using both cluster DFT and periodic cell EHTB methods. Bond order calculations show that Zn preference for the Ca2 vacancy, near the OH channel and with greater structural flexibility, is associated with the formation of a four-fold (bulk) and nearly four-fold (surface) coordination, as in ZnO. When occupying the octahedral Ca1 vacancy, Zn remains six-fold in the bulk, but coordination decreases to five-fold in the surface. In the bulk and surface, Zn2 is found to be more covalent than Zn1, due to a decrease in bond lengths at the four-fold site, which approach the 1.99 Å ZnO value. Zn is however considerably less bound in the biomaterial than in the oxide, where calculated bond orders are twice as large as in HA. Surface phosphate groups (PO4) and hydroxide ions behave as compact individual units as in the bulk; no evidence is found for the presence of HPO4. Ca-O bond orders decrease at the surface, with a consequent increase in ionicity. Comparison between DFT and EHTB results show that the latter method gives a good qualitative account of charge and bonding in these systems.

Original languageEnglish (US)
Article number145502
JournalJournal of Physics Condensed Matter
Issue number14
StatePublished - Jan 1 2010

ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics


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