ABSTRACT
Single crystals of SmAl3(BO3)4 were synthesized by the group growth on seeds method. The crystal structure was solved using a single-crystal experiment and the purity of the bulk material was proved by the Rietveld method. This borate crystallizes in the monoclinic C2/c space group with unit-cell parameters a = 7.2386â (3), b = 9.3412â (5), c = 11.1013â (4)â Å and ß = 103.2240â (10)°. IR and Raman spectroscopic analyses confirmed the monoclinic structure of SmAl3(BO3)4. Under 532.1â nm excitation, luminescence spectra exhibit bands assignable to the transitions from 4G5/2 to 6H5/2, 6H7/2, 6H9/2 and 6H11/2. The similarity of the luminescence spectra of the trigonal and monoclinic polymorphs is explained by the minor role of Sm-O bond distortion and the primary role of rotational distortion of SmO6 octahedra. The smaller covalency of the Sm-O bond in alumoborates is deduced in comparison with galloborates. Calorimetric measurements did not reveal high-temperature structural phase transitions up to a temperature of 720â K.
ABSTRACT
Single crystals of silicon double salt (NH4)3SiF7 = (NH4)2SiF6·NH4F = (NH4)3[SiF6]F were grown and studied by the methods of polarization optics, X-ray diffraction and calorimetry. A sequence of symmetry transformations with the temperature change was established: P4/mbm (Z = 2) (G1) â Pbam (Z = 4) (G2) â P21/c (Z = 4) (G3) â P1[combining macron] (Z = 4) (G4) â P21/c (Z = 8) (G5). Crystal structures of different phases were determined. The experimental data were also interpreted by a group-theoretical analysis of the complete condensate of order parameters taking into account critical and noncritical atomic displacements. Strengthening of the N-HF hydrogen bonds can be a driving force of the observed phase transitions.
