Ab initio study of stability and quadrupole coupling constants in borophosphates.

Abstract

The DFT method was used to predict the formation energies and quadrupole coupling constants CQ in a series of borophosphates: Li3BP2O8, Li2NaBP2O8, Na3BP2O8, Li2B3PO8, Na5B2P3O13, LiNa2B5P2O14 and Na3B6PO13 composed of different networks and different amounts of borate and phosphate units. The change in formation energies with increasing number of B atoms in this series is attributed to the multiplicity of boron sites and is explained by density of states calculations. The calculated CQ values of 7Li, 23Na and 11B are correlated with the coordination and distortion of polyhedra to elucidate the influence of local and more distant environments. As for the CQ of 11B, it should be in the ranges of 0.26-0.36, 0.48-0.84 and ∼1 MHz for boron tetrahedral distortion indices of 0.004-0.013, 0.015-0.019 and 0.033, respectively, whereas CQ ∼3.0 MHz corresponds to boron in a triangular site. The obtained numerical relationships make it possible to predict the quadrupole frequencies for these nuclei based only on their local environment, and vice versa, to propose structural models from NMR data. These results provide guidance for studying similar characteristics of other borophosphates, the structure of which varies depending on the initial reaction, composition and temperature.