Abstract
We combined synchrotron-based infrared absorbance and Raman scattering spectroscopies with diamond anvil cell techniques and a symmetry analysis to explore the properties of multiferroic (NH4)2FeCl5·H2O under extreme pressure–temperature conditions. Compression-induced splitting of the Fe–Cl stretching, Cl–Fe–Cl and Cl–Fe–O bending, and NH4+ librational modes defines two structural phase transitions, and a group–subgroup analysis reveals space group sequences that vary depending upon proximity to the unexpectedly wide order–disorder transition. We bring these findings together with prior high-field work to develop the pressure–temperature–magnetic field phase diagram uncovering competing polar, chiral, and magnetic phases in this system.