Anionic Ordering in Pb$_2$Ti$_4$O$_9$F$_2$ Revisited by Nuclear Magnetic Resonance and Density Functional Theory

Abstract

A combination of $^{19}$F magic angle spinning (MAS) nuclear magnetic resonance (NMR) and density functional theory (DFT) were used to study the ordering of F atoms in Pb$_2$Ti$_4$O$_9$F$_2$. This analysis revealed that F atoms predominantly occupy two of the six available inequivalent sites in a ratio of 73:27. DFT-based calculations explained the preference of F occupation on these sites and quantitatively reproduced the experimental occupation ratio, independent of the choice of functional. We concluded that the Pb atom's 6$s^2$ lone pair may play a role ($\sim$0.1 eV/f.u.) in determining the majority and minority F occupation sites with partial density of states and crystal orbital Hamiltonian population analyses applied to the DFT wave functions.