Influence of atmospheric humidity on the symmetry and phase transitions of layered potassium oxyfluorides K2NbOF5 · H2O

Abstract

Crystals of K2NbOF5 · H2O have been grown, polarization optical investigations have been performed, and the birefringence and rotation angle of the optical indicatrix have been measured in the temperature range 100–400 K. It has been found that, depending on the degree of atmospheric humidity, the layered K2NbOF5 · H2O crystal at room temperature can be in three states, namely, A, B, and C, which differ in symmetry and properties of the crystal. The K2NbOF5 · H2O crystal in the A state exists at a relative humidity RH = 90–100% and undergoes a first-order improper ferroelastic phase transition P $\bar 1$ ↔ C2/m, which is accompanied by strong anomalies of the optical characteristics, twinning, and shear strain x 6 at temperatures T 2 ↓ = 308 K and T 2 ↑ = 313 K. The most stable state of the K2NbOF5 sdH2O crystal is the B state (RH = 20–90%), which retains the monoclinic symmetry C2/m in the temperature range 100–370 K. In a dry atmosphere (RH = 0–20%) or at T 1 ≈ 370 K, the crystal becomes anhydrous (K2NbOF5) with the symmetry P4/nmm (the C state). The difference between the crystals in the states A and B is explained by the presence or absence of water molecules in interlayer spaces.