Structural phase transitions and magnetic superexchange in MIAgIIF3 perovskites at high pressure

TL;DR

This study predicts pressure-induced phase transitions in MIAgIIF3 perovskites up to 100 GPa, revealing different structural changes and magnetic coupling effects depending on the M cation.

Contribution

First theoretical prediction of high-pressure phase transitions in MIAgIIF3 perovskites, detailing structural and magnetic property changes for M = K, Rb, Cs.

Findings

K and Rb compounds undergo orthorhombic-monoclinic-orthorhombic transitions.

Cs compound exhibits a single tetragonal-triclinic transition.

Phase transitions weaken intra-chain antiferromagnetic superexchange.

Abstract

Pressure induced phase transitions of MIAgIIF3 perovskites where M = K, Rb, Cs, have been predicted theoretically for the first time for pressures up to 100 GPa. The sequence of phase transitions for M = K and Rb consists of an orthorhombic to monoclinic and back to orthorhombic transition, associated with progressive bending of infinite chains of corner sharing [AgF6]4 minus octahedra and their mutual approaching via secondary Ag...F contacts. In stark contrast, only a single phase transition i.e. tetragonal to triclinic, is predicted for CsAgF3, associated with substantial deformation of the Jahn Teller-distorted first coordination sphere of AgII and association of the infinite [AgF6]4 minus chains into a polymeric sublattice. The phase transitions markedly decrease the coupling strength of intra-chain antiferromagnetic superexchange in MAgF3 hosts lattices.