Cs 133 Nuclear Magnetic Resonance Study of One-Dimensional Fluctuations in CsH 2 PO 4 and Its Ferroelectric and Antiferroelectric Transitions at High Pressure

Abstract

Pressure and temperature effects on the one dimensional (1D) and higher-dimensionality correlations associated with the ferroelectric and antiferroelectric phase transitions in cesium dihydrogen phosphate were studied by means of the Cs133 nuclear magnetic resonance (NMR) spin-lattice relaxation time T1. We measured T1 at 6.5 MHz at temperatures down to the ferroelectric (FE) Curie point TC at 1 bar and at 1.5 and 3.0 kbar, down to the triple point Tt=124.6 K at 3.3 kbar, and down to the antiferroelectric (AFE) Néel point TN at 3.6 kbar. With decreasing temperature, T1 first decreases exponentially due to 1D fluctuations associated with the Jb interactions in disordered hydrogen-bonded chains running along b. As the temperature falls further, T1 then decreases linearly as the Jc interaction between these chains in hydrogen-bonded planes comes into play. From these results and the known pressure derivatives of TC and TN, we calculated pressure dependences for Jb, Jc, and for the interplanar interaction Ja. At 3.3 kbar Ja changes sign, so the plane stacking becomes AFE instead of FE. Above 8.9 kbar, where Jc extrapolates to zero, a new AFE phase with a checkerboard arrangement of FE b chains is predicted.