Raman scattering and phase transitions in (NH4)(3)TiF7

Gerasimova, Y. V.; Oreshonkov, A. S.; Laptash, N. M.; Krylov, A. S.; Aliev, A. R.; Roginskii, E. M. Source: JOURNAL OF RAMAN SPECTROSCOPY, 49 (7):1230-1235; SI 10.1002/jrs.5374 JUL 2018

Raman spectra of (NH4)3TiF7 within spectral range 10–3,400 cm−1 at temperatures 8–370 K are recorded, which revealed 2 phase transitions at temperatures T1 = 355 K and T2 = 283 K. First principles calculations of lattice dynamics and assignment of the observed lines to specific vibrational types are performed. The first phase transition is classified as an “order–disorder” one. Manifestation of 97 cm−1 vibration (mixed translational [NH4 + F7]) evidences the creation of the hydrogen bond between ammonium group and free fluorine atom, indicating to reconstructive type of phase transition an T2 = 283 K. The emergence of a large number of vibrational lines in Raman spectra at low temperatures proves symmetry lowering of NH4 tetrahedra with the simultaneous ordering of TiF6 octahedra.