The Role of Anharmonicity in (Anti-)Ferroelectric Alkali Niobates

NaNbO₃ (NN), known for the complexity of its phase transition sequence, is antiferroelectric (AFE) at room temperature, while both LiNbO₃ (LN) and KNbO₃ (KN) are ferroelectric (FE). The origin of ferroelectricity in ABO₃ perovskites is believed to lie in the B-O hybridization, but the origin of antiferroelectricity remains unclear. Recent ab initio studies have shown that the same B-O hybridization is necessary in AFE and proposed an additional, anharmonic contribution to the potential of the A-site atom as the crucial difference between FE and AFE perovskites. We used structure factors obtained from X-ray diffraction experiments in combination with the Maximum Entropy Method to obtain electron densities for LN, KN, and NN and identify differences in their bonding behavior. We present experimental evidence for anharmonic A-site contributions of varying strength in alkali niobates, pointing at a new path for the design of (anti-)ferroelectric materials.