Crystalline-field effects on the infrared and Raman spectra of powdered alkali-metal, silver, and thallous nitrates

1970 ◽  
Vol 48 (8) ◽  
pp. 1183-1197 ◽  
Author(s):  
M. H. Brooker ◽  
D. E. Irish

Infrared and Raman spectra have been recorded for room-temperature-phase, powdered samples of LiNO3, NaNO3, KNO3, RbNO3, CsNO3, AgNO3, and TlNO3. For the trigonal systems, the nitrate pairs LiNO3, NaNO3 and RbNO3, CsNO3 give almost identical spectra. For the orthorhombic systems, AgNO3 and TlNO3 give similar spectra, whereas that of KNO3 is significantly different. Site and correlation field perturbations are considerably more pronounced in the antisymmetric stretching region (ν3 ca. 1400 cm−1) than in the antisymmetric bending region (ν4 ca. 700 cm−1). Although lifting of the degeneracy of E′ modes was frequently observed, the reported split of the ν4(E′) mode (ca. 716 cm−1) of the aragonite form of KNO3 could not be confirmed. Multiple internal reflectance techniques have been employed to observe the extremely intense ν3(E′) infrared fundamental ca. 1400 cm−1.

1973 ◽  
Vol 51 (3) ◽  
pp. 402-404 ◽  
Author(s):  
A. Bree ◽  
R. A. Kydd ◽  
V. V. B. Vilkos ◽  
R. S. Williams

A study of the polarized infrared and Raman spectra of acenaphthylene single crystals has been made. These results, together with Gordon and Yang's preliminary X-ray work, suggest that the molecules pack in some disordered arrangement in the solid at room temperature. Most of the A1 fundamentals were identified in the Raman solution spectrum from their low depolarization ratio, and a few tentative assignments of nontotally symmetric fundamentals were made.


2003 ◽  
Vol 2003 (8) ◽  
pp. 518-521 ◽  
Author(s):  
M.K. Marchewka

Room temperature powder infrared and Raman measurements for the new melaminium salt, bis(2,4,6-triamino-1,3,5-triazin-1-ium) sulfate dihydrate, 2C3H7N6+·SO42-·2H2O, in the crystalline state, were carried out. The vibrational spectra in the region of internal vibrations of the ions corroborate recent X-ray data of Janczak et al. Some spectral features of this new crystal are referred to those of other crystalline melaminium salts.


1971 ◽  
Vol 49 (8) ◽  
pp. 1289-1295 ◽  
Author(s):  
M. H. Brooker ◽  
D. E. Irish

Infrared and Raman spectra of solid LiNO2•H2O, LiNO2, NaNO2, KNO2, and CsNO2 are presented and discussed. Pronounced changes in the spectra of LiNO2•H2O during dehydration to anhydrous LiNO2 are interpreted as evidence for an ordered distribution of NO2− ions over two non-equivalent sites (akin to linkage isomerism) in anhydrous LiNO2. The frequencies of the internal modes of the nitrite ion shift to lower values with increasing cation size. Vibrational bands due to nitrate ion present as an impurity are assigned.


Author(s):  
Viktor Stefov ◽  
Violeta Koleva ◽  
Metodija Najdoski ◽  
Adnan Cahil ◽  
Zuldjevat Abdija

Fourier transform infrared (FT-IR) spectra recorded at room temperature (RT) and at the boiling temperature of liquid nitrogen (LNT), as well as Raman spectra recorded at room temperature for the cubic polymorph of magnesium cesium arsenate hexahydrate (MgCsAsO4·6H2O) and its partially deuterated analogues, were interpreted with respect to the normal modes of the water molecules and the arsenate ions and water librations. The spectral characteristics of MgCsAsO4·6H2O were compared to the cubic form of the phosphate analogue. A spectral similarity between the two isostructural salts was established, except for the obvious differences due to the nature of the anions (AsO43– vs PO43–). The spectroscopic data for the uncoupled OD stretching mode of the matrix-isolated HDO molecules revealed that the hydrogen bonds formed in the arsenate salt were stronger than those in the phosphate. In the Raman spectrum of the protiated compound, only one very intensive band at 811 cm–1 was observed in the region of the stretching vibrations of the AsO43– ion, which was insensitive to deuteration. In accordance with the expectation, one band appeared in the same spectral range in the infrared spectra of the protiated and highly deuterated sample at 792 cm–1 and 810 cm–1, respectively, which can be attributed with certainty to the asymmetric stretching ν3(AsO4) modes.


1998 ◽  
Vol 51 (4) ◽  
pp. 311 ◽  
Author(s):  
Graham A. Bowmaker ◽  
Jack M. Harrowfield ◽  
Aaron M. Lee ◽  
Brian W. Skelton ◽  
Allan H. White

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for the title compounds, [bpyH]+[(bpy)BiX4]-, X = Cl, Br, the chloride being obtained in a second acetonitrile- sesquisolvated form. [bpyH]+[(bpy)BiX4]-, X = Cl, Br, are isomorphous, monoclinic C2/c, a ≈ 15·3, b ≈ 9·6, c ≈ 16·8 Å, β 109°, Z = 4, conventional R on |F| being 0·056, 0·059 for No 1456, 769 independent ‘observed’ (I > 3σ(I)) reflections respectively. [bpyH] [(bpy)BiCl4].1½MeCN is monoclinic, P21/m, a 9·572(2), b 34·521(8) c 8·218(2) Å, β 102·13(2)°, Z = 4, R 0·043 for No 2635. All anionic species are mononuclear, the bismuth being quasi-octahedral. Bands in the far-infrared and Raman spectra due to the vibrations of the N2BiCl4 core in [(bpy)BiCl4]- are assigned, and their relationship to the vibrations of [BiCl6]3- is discussed.


1998 ◽  
Vol 51 (4) ◽  
pp. 285 ◽  
Author(s):  
Graham A. Bowmaker ◽  
Jack M. Harrowfield ◽  
Peter C. Junk ◽  
Brian W. Skelton ◽  
Allan H. White

Room-temperature single-crystal X-ray studies are recorded for some dimethyl sulfoxide (dmso) solvates of bismuth(III) bromide and iodide. Colourless BiBr3.3dmso is triclinic, P-1, a 8·467(4), b 9·109(4), c 13·901(4) Å, α 76·34(4), β 76·95(4), γ 64·56(4)°, Z = 2; conventional R on |F| was 0·050 for No 2306 independent ‘observed’ (I > 3σ(I)) reflections. The complex is mononuclear with a quasi-octahedral fac-bismuth environment, [(dmso-O)3BiBr3], isomorphous with the previously determined chloride. Orange BiI3-2dmso is triclinic, P-1, a 12·558(2), b 8·962(2), c 8·342(1) Å, α 61·85(1), β 78·27(1), γ 76·89(2)°, Z = 2 f.u., R 0·048 for No 1953. The complex is binuclear, a pair of iodide atoms bridging the two bismuth atoms, [(dmso-O)2I2Bi(µ-I)2BiI2(O-dmso)2]; the two O-dmso ligands about each six-coordinate bismuth lie trans. Red BiI3.2 ⅔ dmso is triclinic, P-1, a 16·435(6), b 14·926(2), c 12·396(3) Å, α 74·89(2), β 73·24(2), γ 79·18(2)°, Z = 6, R 0·059 for No 5858. The complex is [Bi(O-dmso)8] [Bi2I9], the eight-coordinate metal environment of the cation being, unusually, dodecahedral; in the anion a pair of quasi-octahedral six-coordinate bismuth atoms are bridged by three iodides, [I3Bi(µ-I)3BiI3]3-. Bands in the far-infrared and Raman spectra due to the v(BiX) modes are assigned and discussed in relation to the structures of the complexes. The assignment of the v(BiO) modes is discussed.


1991 ◽  
Author(s):  
R. J. Meilunas ◽  
R. P. Chang ◽  
S. Liu ◽  
M. M. Kappes

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