Theoretical prediction of some layered Pa2O5 phases: structure and properties†
Density functional theory (DFT) was used to predict and study protactinium pentoxide (Pa2O5), which presents a fluorite and layered protactinium oxide-type structure. Although the layered structure has been observed with the isostructural transition Nb and Ta metal pentoxides experimentally, the detailed structure and properties of the layered Pa2O5 are not clear and understandable. Our theoretical prediction explored some possible stable structures of the Pa2O5 stoichiometry according to the existing M2O5 structures (where M is an actinide Np or transition Nb, Ta, and V metal) and replacing the M ions with protactinium ions. The structural, mechanical, thermodynamic and electronic properties including lattice parameters, bulk moduli, elastic constants, entropy and band gaps were predicted for all the simulated structures. Pa2O5 in the β-V2O5 structure was found to be a competitive structure in terms of stability, whereas Pa2O5 in the ζ-Nb2O5 structure was found to be the most stable overall. This is consistent with Sellers's experimental observations. In particular, Pa2O5 in the ζ-Nb2O5 structure is predicted to be charge-transfer insulators. Furthermore, we predict that ζ-Nb2O5-structured Pa2O5 is the most thermodynamically stable under ambient conditions and pressure.