The mechanism of phase transitions in azide perovskites probed by vibrational spectroscopy.

The temperature-dependent IR and Raman spectroscopy has been used to study the phase transitions in manganese-azide frameworks with either dimethylammonium (DMA+) or tetramethylammonium (TMA+) cations which adopt a perovskite-like crystal structure. The phase transition in DMA-analogue seems to be associated with cooperative tilting of MnN6 octahedra and order-disorder of hydrogen bonds while in TMA-analogue it is more complex and composed of several processes, including the motions of both manganese-azide framework and tetramethylammonium cations and their possible coupling. Our results are in agreement with the data received from crystallographic and dielectric measurements in the case of TMA-analogue and we have demonstrated the importance of order-disorder of hydrogen bonds in the case of DMA-analogue which previously has not been taken into account.