Vibrational spectroscopy of the borate mineral henmilite Ca₂Cu[B(OH)₄]₂(OH)₄.
Henmilite is a triclinic mineral with the crystal structure consisting of isolated B(OH)(4) tetrahedra, planar Cu(OH)(4) groups and Ca(OH)(3) polyhedra. The structure can also be viewed as having dimers of Ca polyhedra connected to each other through 2B(OH) tetrahedra to form chains parallel to the C axis. The structure of the mineral has been assessed by the combination of Raman and infrared spectra. Raman bands at 902, 922, 951, and 984 cm(-1) and infrared bands at 912, 955 and 998 cm(-1) are assigned to stretching vibrations of tetragonal boron. The Raman band at 758 cm(-1) is assigned to the symmetric stretching mode of tetrahedral boron. The series of bands in the 400-600 cm(-1) region are due to the out-of-plane bending modes of tetrahedral boron. Two very sharp Raman bands are observed at 3559 and 3609 cm(-1). Two infrared bands are found at 3558 and 3607 cm(-1). These bands are assigned to the OH stretching vibrations of the OH units in henmilite. A series of Raman bands are observed at 3195, 3269, 3328, 3396, 3424 and 3501 cm(-1) are assigned to water stretching modes. Infrared spectroscopy also identified water and OH units in the henmilite structure. It is proposed that water is involved in the structure of henmilite. Hydrogen bond distances based upon the OH stretching vibrations using a Libowitzky equation were calculated. The number and variation of water hydrogen bond distances are important for the stability off the mineral.
A vibrational spectroscopic study of perhamite, an unusual silico-phosphate.
The silico-phosphate mineral perhamite has been studied using a combination of electron and vibrational spectroscopy. SEM photomicrographs reveal that perhamite morphology consists of very thin intergrown platelets that can form a variety of habits. Infrared spectroscopy in the hydroxyl-stretching region shows a number of overlapping bands which are observed in the range 3581-3078 cm(-1). These wavenumbers enable an estimation to be made of the hydrogen bond distances in perhamite: 3.176(0), 2.880(5), 2.779(6), 2.749(3), 2.668(1) and 2.599(7)A. Intense Raman bands are observed in the region 1110-1130 and 966-996 cm(-1) and are assigned to the SiO(4) and PO(4) symmetric stretching modes. Other bands are observed in the range 1005-1096 cm(-1) and are attributed to the nu(3) antisymmetric bending modes of PO(4). Some low intensity bands around 874 cm(-1) were discovered and remain unclassified. Bands in the low-wavenumber region are assigned to the nu(4) and nu(2) out-of-plane bending modes of the OSiO and PO(4) units. Raman spectroscopy is a useful tool in determining the vibrational spectroscopy of mixed hydrated multi-anion minerals such as perhamite. Information on such a mineral would be difficult to obtain by other means.
Reorientational motion of hydroxide ions in solid RbOH and CsOH
Abstract The temperature dependence of the O (H,D)− stretching modes (frequencies, halfwidths, IR, Raman) of polymorphic RbOH and CsOH is studied in terms of hydrogen bonding, disorder of hydroxide ions, and phase transitions. The different νOD frequencies of isotopically dilue samples (RbOH mon. I and CsOH o-rh. II) in the IR and Raman spectra and the unusually large positive temperature shifts of these bands are interpreted as due to order—disorder transitions from hydrogen-bnded OH− ions in the low-temperature polymorphs to non-H-bonded ions in the room temperature modifications. The halfwidths of the O (H,D)− bands exhibit an Arrhenius type behaviour. In the deuterated compounds there are stronger hydrogen bonds (D-bonds) than in the non-deuterated samples (H-bonds). These findings are attributed to the greater hydrogen bond acceptor strength of OD− than that of OH−. In KBr discs, hitherto unknown isostructural hydroxide bromides of caesium and rubidium are formed.