Antiferroelectrics have potential applications in energy conversion and storage, but are scarce, particularly among oxides that otherwise display rich ferroic behaviours. A question then arises whether potential antiferroelectrics are being overlooked, simply because their corresponding ferroelectric phase has not been discovered yet. Here we report a first-principles study suggesting that this is the case for a family of ABO₃ pyroxene-like materials, characterised by chains of corner-sharing BO₄ tetrahedra, a well-known member being KVO₃. The irregular tetrahedra have an electric dipole associated to them. In the most stable polymorph, the dipoles display an antipolar pattern with zero net moment. However, upon application of an electric field, half of the tetrahedra rotate, flipping the corresponding dipoles and reaching a ferroelectric state. We discuss the unique possibilities for tuning and optimisation of antiferroelectricity that these materials offer. We suggest that the structural features enabling this antiferroelectric behaviour can also be found in other all-important mineral families.

反铁电体在能量转换和存储中具有潜在的应用，但是稀缺，尤其是在氧化物中，否则这些氧化物会表现出丰富的铁性行为。然后产生一个问题，是否仅由于尚未发现潜在的反铁电体相应的铁电相而被忽略。在这里，我们报告了一项第一性原理研究，表明一类A BO ₃辉石状材料就是这种情况，其特征是角共享B O ₄四面体链，著名的成员是KVO ₃。不规则四面体具有与其相关的电偶极子。在最稳定的多晶型物中，偶极子显示出具有零净矩的反极性图形。然而，在施加电场时，四面体的一半旋转，翻转相应的偶极子并达到铁电状态。我们讨论了这些材料提供的反铁电优化和优化的独特可能性。我们建议使这种反铁电行为的结构特征也可以在其他所有重要的矿物家族中找到。