Infrared absorption spectra of As-Se glasses

IR absorption spectra of As-Se glasses have been studied over a wide range of compositions. Various two-phonon, multiphonon (combination tones) and impurity absorptions have been identified. Compositional variation of relative band intensities has been explained in terms of the chemically ordered network model.

Infrared absorption spectra of single crystals of glycine silver nitrate and monoglycine nitrate

he infrared absorption spectra of glycine silver nitrate (GAgNO3) and glycine nitrate (GHNO3) show that the glycine group exists completely in the zwitter ion form in the former and in both forms in the latter. The spectrum of GAgNO3 at liquid air temperature did not reveal any striking change which can be attributed to a freezing of the rapid reorientation of the NH3+ group taking place at higher temperatures. The position of the COO− stretching frequencies indicate that this group is co-ordinated only weakly to the Ag+ ion. The summation frequencies reported by Schroeder, Wier and Lippincott (1962) for AgNO3 were not observed in the present study on GAgNO3. It shows however that ferroelectricity in GAgNO3 is in all probability due to the motion of the Ag+ ion in the oxygen co-ordination polyhedron and is not directly connected with the ordering of the hydrogen bonds below Curie point.

Infrared absorption studies on some derivatives of xanthic, dithiocarbamic and trithiocarbonic acids

The infrared absorption spectra of some of the derivatives of xanthic Image dithiocarbamic Image and trithiocarbonic Image acids are studied in the sodium chloride optics region and the bands assigned to group frequencies. The position of C---O---C and C=S bands in the derivatives of xanthic acid has been discussed from theoretical and experimental evidences and it is suggested that the two strong bands around 1200 and 1030 cm−1 are due to the Image group. The bands around 980 and 1050 cm−1 in the derivatives of dithiocarbamic and trithiocarbonic acids respectively have been assigned to C=S group frequencies. These bands shift to lower frequency in the corresponding ionic compounds while the bands around 1030 and 1200 cm−1 in the ionic compounds of xanthic acid shift to higher and lower frequencies respectively.

Direct Infrared Absorption Spectroscopy of Benzene Dimer

The direct infrared (IR) absorption spectrum of benzene dimer formed in a free-jet expansion was recorded in the 3.3 mu m region for the first time. This has led to the observation of the C H stretching fundamental mode nu(13) (B(1u)), which is both IR and Raman forbidden in the monomer. Moreover, the IR forbidden and Raman allowed nu(7) (E(2g)) mode has been observed as well. These two modes were found to be red-shifted along with the IR allowed nu(20) (E(1u)) mode, as previously reported by Erlekam et al. [Erlekam; Frankowski; Meijer; Gert von Helden J. Chem. Phys. 2006, 124, 171101], using ion-dip spectroscopy, contrary to the blue-shift predicted earlier by theoretical studies. The observation of the nu(13) band indicates that the symmetry is reduced in the dimer, confirming the T-shaped structure observed by Erlekam et al. Our experimental results have not provided any direct evidence for the presence of the parallel displaced geometry, the main objective of the present work, as predicted by theoretical calculations.

Simulation of the infrared spectra of thioacetamide by the extended molecular mechanics method

The infrared spectrum of the matrix-isolated species of thioacetamide has been simulated using the extended molecular mechanics method. The equilibrium structure, vibrational frequencies, dipole moment and infrared absorption intensities of thioacetamide have been calculated in good agreement with the experiment. The vibrational frequencies and infrared absorption intensities for the isotopic molecules (CH2CSNH2)-C-13, (CH3CSNH2)-N-15 and (CH2CSND2)-C-13 have also been calculated consistent with the experiment. The infrared spectra of the matrix isolated species of N- and C- deuterated isotopomers of thioacetamide, CH3CSND2 and CD3CSNH2 have also been simulated in satisfactory agreement with the experimental spectra.

Simulation of the infrared spectra of N-methylformamide and N-methylacetamide by the extended molecular mechanics method

The infrared spectra of the matrix isolated species of N-methylformamide (NMF) and N-methylacetamide (NMA) and their N-deuterated molecules have been simulated by the extended molecular mechanics method using an empirical force field which includes charges and charge fluxes as coulombic potential parameters. The structural parameters and dipole. moments of NMF and NMA have. also been computed in satisfactory agreement with the experiment. Good agreement between experimental and calculated vibrational frequencies and infrared absorption band intensities for NMF and NMA and their deuterated molecules has been obtained. The vibrational assignments of NMF and NMA are-discussed taking also into account the infrared absorption intensities.

Mössbauer studies of the corrosion products of iron formed in aqueous ammonium nitrate solution

The products of corrosion reaction of electrolytic iron in 45% ammonium nitrate solution formed under various conditions of time, temperature and pH have been analysed mainly by Mössbauer spectroscopy, in combination with X-ray diffraction, infrared absorption and electron microscopy techniques. γ-Fe00H is found to be the major product of hydrolytic precipitation at pH > 5.6 while only α-FeOOH is formed at pH < 3.0. In the pH range 3.0 < pH < 5.0, α-Fe00H and ferrihydrite are both formed. However, once the nuclei of α-Fe00H are formed under low pH conditions, their growth is favoured even in the otherwise unfavourable slightly acidic medium, resulting in a hydrous α-Fe00H which has two distinct hyperfine fields at the 57Fe nucleus. Magnetite is always formed in the vicinity of the metal and its rate of formation on the surface increases with temperature. α-Fe203 is the major product of hydrolytic precipitation at temperatures >80C. The possible mechanisms for the formation of each of the corrosion products are discussed.

X-ray and IR characterisation of Nasicon solid solution, Na1+xZr2SixP3−xO12

X-ray and IR studies on Nasicon solid solutions, Na1+xZr2SixP3−xO12, are carried out as a function of composition x. X-ray diffraction studies show that the unit cell volume increases as x increases and exhibits a maximum at x ≈ 2. On further increase in x the unit cell volume decreases. The infrared absorption peak positions and the splitting of these absorption peaks suggest a distortion of the PO4 and SiO4 tetrahedra. But the distortion is not large enough to change the local symmetry around the phosphorus or silicon ion from Td to C3v.

Thermal reactivity of metal acetate hydrazinates

Metal acetate hydrazinates, M(CH3COO)2(N2H4)2 (M = Mn, Co, Ni, Zn, Cd) have been prepared and characterized by chemical analysis and infrared absorption spectra. Thermal decomposition of the complexes has been studied using simultaneous TG-DTG-DTA technique. Metal acetate hydrazinates decompose exothermically through metal acetate intermediates to the respective metal oxides.

Vibrational spectra and ferroelectric transition in sodium ammonium selenate dihydrate

The Raman and infrared absorption spectra of sodium ammonium selenate dihydrate (SASD) have been recorded both above and below the ferroelectric transition temperature. The deuterated SASD has also been investigated. The results support the view that while there is only one type of NH4+ ions in the para electric phase, there are two types of NH4+ ions below Tc. The water molecules undergo considerable change and non-equivalent O-H bonds are produced below Tc. The SeO2/4- ions undergo very little change.

Laser Raman spectroscopic study of ferroelastic LiCsSO4

Lithium caesium sulphate has been reported to undergo a phase transition from the room temperature orthorhombic phase with space groupP cmn to a final phase with space groupP 22/n. Though a sharp anomaly in its physical properties has been found at 202.0;K, it was found that there was a need for careful investigations in the vicinity of 240 and 210.0;K. Since the changes in the crystal structure involve primarily a rotation of the SO4 tetrahedron about thec-axis and as this may be reflected both in the intensity and polarisation of the internal as well as external phonon modes, the laser Raman spectra of oriented single crystals of LiCsSO4 at different temperatures were investigated. For correlation and definite identification of the spectral features, its infrared absorption spectrum was also studied. An analysis of the intensities and polarizations of the internal modes of the sulphate ions reveals the change in symmetry of the crystal. The integrated intensity and peak height of thev 1 line, plotted against temperature show anomalous peaks in the region of the phase transition. Differential scanning calorimetric study gives the enthalpy change ΔH across the phase transition to be 0.213 kJ/mol.

Vibration spectra of ferroelectric alkali trihydrogen selenites and the nature of the hydrogen bond potential in these crystals

Raman spectra of the ferroelectric LiH3 (SeO3)2 and NaH3(SeO3)2 and the anti-ferroelectric KH3 (SeO3)2 have been recorded at room temperature using a He-Ne and also an Ar-ion laser source. The infrared absorption spectra of these crystals and their deuterated analogues have been recorded in the region 400–4000 cm−1 both below and above the Curie temperature. From an analysis of the spectrum in the region 400–900 cm−1 it is concluded that (i) in LiH3 (SeO3)2 the protons are ordered in an asymmetric double minimum potential with a low barrier and the spectrum can be interpreted in terms of HSeO3− and H2SeO3 vibrations, (ii) in NaH3 (SeO3)2 all three protons occupy a single minimum potential at room temperature and below the transition temperature the groups HSeO3− and H2SeO3 are present, (iii) the proton at the inversion centre in KH3(SeO3)2 is in a broad troughed potential well and the low temperature spectrum is more likely to be due to H3SeO3+ and SeO32− species. This deviation of the spectrum from that of the previous two crystals is attributed to the difference in H-bond scheme and hence the absence of any cooperative motion of protons in this crystal.

Conformationally restricted formyl methionyl tripeptide chemoattractants: a three-dimensional structure-activity study of analogs incorporating a C alpha,alpha-dialkylated glycine at position 2

The conformationally restricted CHO-L-Met-Xxx-L-Phe-OY (where Xxx = Aib, Ac3c, Ac5c, Ac6c, and Ac7c; Y = H, Me) tripeptides, analogs of the chemoattractant CHO-L-Met-L-Leu-L-Phe-OH, have been synthesized in solution by classical methods and fully characterized. Compounds were compared to determine the combined effect of backbone conformational preferences and side-chain bulkiness on the relation of three-dimensional structure to biological activity. Each peptide was tested for its ability to induce granule enzyme secretion from rabbit peritoneal polymorphonuclear leukocytes. In parallel, a conformational analysis on the CHO-blocked peptide and their tertbutyloxycarbonylated synthetic precursors was performed in the crystal state and in solution using X-ray diffraction, infrared absorption, and 1H nuclear magnetic resonance. The biological and conformational data are discussed in relation to the proposed model of the chemotactic peptide receptor of rabbit neutrophils.

Molecular model for localised modes in zincblende structures

A molecular model for substitutional defects in a zincblende lattice has been worked out. The infrared absorption due to A1 in InSb and Li in GaAs are interpreted on the basis of this model.

Raman spectrum of strontium titanate

The Raman spectrum of strontium titanate has been recorded using λ 4358 of mercury as exciter. The observed spectrum consists of 7 Raman lines, one of which is of low frequency, as expected from the recent theory of Cochran. 6 of these Raman lines have been interpreted as the first order spectrum arising from a small deviation of the cubic strontium titanate from its idealized symmetry. It has been shown that one normal mode of SrTiO3 neglected by J.T. Last, will be really active in infrared absorption in the region of 440 cm-1 and that it has to be taken into account in the interpretation of the infrared spectra of titanates. The four vibrational modes of the unit cell of SrTiO3 correspond to frequencies of 90, 335, 441 and 620 cm-1 observed in Raman effect. The large width of the Raman lines and the additional lines at 256 cm-1 and 726 cm-1 have been attributed to a splitting of the longitudinal and transverse optical modes. With the observed frequencies it has been found possible to account for in a satisfactory manner the specific heat of SrTiO3 in the range 54·84° K to 1800° K.