First-principles based theoretical calculations of atomic structures of hydroxyapatite surfaces and their charge states in contact with aqueous solutions

values for the {0001} surface and the Ca-rich {101̄0} surface were obtained to be 4.8 and 8.7, respectively. This indicates that in an aqueous solution at neutral pH, the {0001} and Ca-rich {101̄0} surfaces are negatively and positively charged, respectively. This trend agrees with experimental data from chromatography and zeta potential measurements. Our methodology based on first-principles calculations enables determining macroscopic charge states of HAp surfaces from atomic and electronic levels.