New Ideas for Understanding the Structure and Magnetism in AgF(2): Prediction of Ferroelasticity

In the search for new high‐temperature superconductors, it has been proposed that there are strong similarities between the fluoroargentate AgF(2) and the cuprate La(2)CuO(4). We explored the origin of the possible layered structure of AgF(2) by studying its parent high‐symmetry phase and comparing these results with those of a seemingly analogous cuprate, CuF(2). Our findings first stress the large differences between CuF(2) and AgF(2). Indeed, the parent structure of AgF(2) is found to be cubic, naturally devoid of any layering, even though Ag(2+) ions occupy trigonal sites that, nevertheless, allow the existence of a Jahn‐Teller effect. The observed Pbca orthorhombic phase is found when the system is cooperatively distorted by a local E⊗e trigonal Jahn‐Teller effect around the silver sites that creates both geometrical and magnetic layering. While the distortion implies that two Ag(2+)−F(−) bonds increase their distance by 15 % and become softer, our simulations indicate that covalent bonding and interlayer electron hopping is strong, unlike the situation in cuprate superconductors, and that, in fact, exfoliation of individual planes might be a harder task than previously suggested. As a salient feature, these results prove that the actual magnetic structure in AgF(2) is a direct consequence of vibronic contributions involved in the Jahn‐Teller effect. Finally, our findings show that, due to the multiple minima intrinsic to the Jahn‐Teller energy surface, the system is ferroelastic, a property that is strongly coupled to magnetism in this argentate.