Variation of the Raman frequency of a soft mode with the pressure (20 oC) for the phase transitions in NH4F

The Raman frequency of a soft mode (238 cm-1) is analyzed as a function of pressure at 20 oC for NH4F using the experimental data from the literature. This analysis is performed for the pressure dependence of the Raman frequency shifts (1/n)(¶n/¶P)T of the soft mode close to the I - III, III - V and V – VI transitions in NH4F. The frequency shifts increase as the pressure increases toward the phase transitions at T = 20 oC (293 K) in this ammonium structure. From the frequency shifts of the soft mode studied, the pressure dependence of the isothermal compressibility is predicted through the mode Grüneisen parameter. Our calculated isothermal compressibility can be compared with the experimental measurements.

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  • [1] Raghurama G, Narayan R. The structures of the ammonium halides. J Phys Chem Solids 1983; 44: 633-638.
  • [2] Levy HA, Peterson SW. Neutron diffraction study of the crystal structure of ammonium chloride. Phys Rev 1952; 86: 766.
  • [3] Stevenson R. Phase transitions in the ammonium halides. J Chem Phys 1961; 34: 1757.
  • [4] Pistorius CWFT. Melting curves and phase transitions of the ammonium halides to 40 kbar. J Chem Phys 1969; 50: 1436.
  • [5] Zou G, Zhao Y, Cui O, Jin Z. Raman spectra and phase transitions of NH4F at high pressure. Solid State Physics Under Pressure. In: Mimonura S (Ed.) Terra Scientific Publishing Company, 1985. pp. 191.
  • [6] Salihoğlu S, Yurtseven H, Enginer Y. P-T phase diagram for NH4F. Solid State Sciences 2002; 4: 529-534.
  • [7] Swenson CA, Tedeschi JF. Phase transitions in ammonium fluoride. J Chem Phys 1964; 40: 1141.
  • [8] Nabar MA, Calvert LD, Whalley E. J Chem Phys 1989; 91: 1353.
  • [9] Wyckoff RGW. Crystal Structure. Interscience Publishers Inc., New York, 2nd ed. Vol. 1, 1963.
  • [10] Pistorius CWFT. Progress in Solid State Chemistry vol 11, 1976 ed. McCaldin JO, Somorja G. New York: Permagon. pp. 11.
  • [11] Glazkov VP, Kozlenko DP, Savenko, BN et al. Neutron diffraction study of structural variations in NH4I and NH4F ammonium halides under high pressures. Crystallogr Rep 1999; 44: 50.
  • [12] Glazkov VP, Kozlenko DP, Savenko BN, Somenkov VA. Vibrational spectra of the ammonium halides NH4I and NH4F at high pressures. J Exp Theo Phys 2000; 90: 319-323.
  • [13] Tikhomirova GV, Babushkin AN. Ammonium halides NH4Cl, NH4F and NH4Br under high pressure. Phys Stat Sol (b) 2003; 235: 337-340.
  • [14] Tikhomirova GV, Babushkin AN. High pressure induced phase transition dynamics in ammonium halides. Joint 20th AIRAPT- 43th EHRG, 2005 Karlsruhe, Germany.
  • [15] Durig JR, Antion DJ. Far infrared and Raman spectra of ammonium fluoride and ammonium fluoride-d4. App Spectroscopy 1970; 24: 16.
  • [16] Wong PTT, Whalley E. A technique for the Raman spectroscopy of high pressure phases recovered at low temperatures. The low frequency Raman spectrum of ammonium fluoride II. Rev Sci Inst 1972; 43: 935.