Effect of Deuteration on Phase Transitions in Vanadium Dioxotetrafluoride

Bogdanov, E., V; Pogoreltsev, E., I; Gorev, M., V; Molokeev, M. S.; Flerov, I. N. Source: PHYSICS OF THE SOLID STATE, 61 (2):192-200; 10.1134/S1063783419020082 FEB 2019

The crystals of (ND4)3VO2F4 with a high degree of deuteration (~87%) have been grown and a significant (~1.5%) increase in the unit cell volume has been detected. The decrease in the chemical pressure leads to a change in the sequence of phase transitions due to wedging-out of one of the rhombic phases observed in (NH4)3VO2F4. The thermal physical studies have been carried out and the entropies, deformations, and pressure coefficients related to structural transformations have been determined. The Tp phase diagram has been built and the pressure and temperature boundaries of crystal phase stability have been determined. The dielectric studies demonstrate a nonferroelectric nature of the phase transitions in (ND4)3VO2F4. The experimental and model entropies are compared. Based on the decrease in the entropy as a result of deuteration, a hypothesis on significant but not limited anharmonism of vibrations of ammonia tetrahedral corresponding to the disordering is proposed.