Stability of Hydroxo/Oxo/Fluoro Zirconates vs. Hafniates—A DFT Study

We performed density functional theory (DFT) calculations on binary and ternary oxo/fluoro crystals of the geochemical twin pair zirconium hafnium to evaluate compare their stabilities. This is first DFT study bulk ZrF4 or HfF4, as well a hypothetical ZrOF2 HfOF2 crystal. For α-MO2, β-MF4 MOF2, we have found significantly higher cohesive energies for respective species. suggests considerable gap in affinity toward fluorine oxygen between solid state. In agreement with experimental findings, this slightly more pronounced fluorine. also theoretical, endothermic mono-hydroxylation fluorides oxyfluorides model difference fluoride versus hydroxide. these, could find slight energetic preference compound.