Dielectric phase transition and symmetry change of constituent molecules in proton-deuteron mixed crystals of squaric acid

We have investigated effects of random substitution of proton sites with deuterons on the temperature‐ and pressure‐induced phase transitions in squaric acid crystal, which consists of ferroelectrically ordered molecular sheets of [C4O4]2−(SQ2−) skeletons and intervening protons or deuterons. In the isotopically mixed crystals (H1−xDx )2SQ, the critical temperature Tc for the dielectric phase transition was found to increase linearly with the deuterium concentration x, while the critical pressure Pc increases nonlinearly with x at 300 K. Around the pressure ∼20 kbar above Pc, the constituent SQ2− skeletons in the paraelectric phase show a symmetry change from the asymmetric (C1h ) to centrosymmetric (C4h ) form, which is likely caused by the deformation of the correlated proton (deuteron) potential.