Low-temperature anomalies of infrared band intensities and high-pressure behavior of edingtonite

Abstract

Edingtonite is a ferroelectric material of the Rochelle salt (RS) class and shows large anomalies of different properties in the temperature range of −53 to −133 °C. Classical RS exhibits the low-temperature phase transition P2 12 12– P2 111, whereas ammonium RS shows the phase transition P2 12 12– P1 12 11. According to our data, edingtonite blocks this possible symmetry lowering by the phase transition P2 12 12– P112. Edingtonite, similarly to RS crystals, has two sub-lattices of water molecules and exhibits a complex low-temperature behavior. There are at least three anomalies in the low-temperature dependence of the generation of the second optical 0.53-micron harmonics, excited by the 1.06-micron line of a Nd pulse laser. Edingtonite also exhibits significant anomalies in the low-frequency range of its IR spectrum at low temperatures. The maximum IR anomaly is observed in natural edingtonite at −124 °C, whereas in the deuterated sample the same anomaly occurs at −113 °C. The most intense anomalous broad band at 220 cm −1 did not shift due to deuteration. According to the presented lattice-dynamical calculations, this vibration corresponds to a strong deformation of the cavity around the water molecules during the phase transition. Raman study of edingtonite under high pressure in a diamond anvil cell (DAC) at room temperature shows that there is no pressure-induced phase transition up to 6.4 GPa. No amorphization was observed at this pressure range.