The nature of the structural phase transition in the quantum magnets barlowite, Cu4(OH)6FBr, and claringbullite, Cu4(OH)6FCl was investigated. These materials consist of parallel-stacked Cu2+ kagome layers, separated by planes that contain Cu2+ cations and halide anions. The structural transition is of an order-disorder type, where at ambient temperature the interlayer Cu2+ ions are disordered over three equivalent positions. In barlowite, the dynamic disorder becomes static as the temperature is decreased, resulting in a lowering of the overall symmetry from hexagonal P63/mmc to orthorhombic. The dynamic disorder in claringbullite persists to lower temperatures, with a transition to orthorhombic space group Pnma observed in some samples. Ab initio density functional theory calculations explain this temperature-dependent structural phase transition and provide additional insights regarding the differences between these two materials.
supportingInfo chemarxiv 20181214