Vibrational spectroscopy and quantum chemical studies of 1,6,7,12,13,18-hexaazatrinaphthylene and related compounds

The spectral properties of 1,6,7,12,13,18-hexaazatrinaphthylene (HATN) and a number of related compounds are modeled using density functional theory, B3LYP. The calculations predict the frequencies with mean absolute deviation of 6 cm(-1) and there is little improvement on going to basis sets larger than 6-31 G(d). The substituent effects on the observed spectra are modeled effectively in both frequency shifts and relative intensities. The electronic properties may be predicted using TD-DFT and these are in very good agreement, in terms of transition energies and intensities, with the experimental data.     

Vibrational spectroscopy of resveratrol

In this article the authors deal with the experimental and theoretical interpretation of the vibrational spectra of trans-resveratrol (3,5,4'-trihydroxy-trans-stilbene) of diverse beneficial biological activity. Infrared and Raman spectra of the compound were recorded; density functional calculations were carried out resulting in the optimized geometry and several properties of the molecule. Based on the calculated force constants, a normal coordinate analysis yielded the character of the vibrational modes and the assignment of the measured spectral bands.     

Vibrational spectroscopy of implants

The results of systematic spectral studies of polymers in ophthalmology are presented. The spectral criteria of selection of intraocular lens (IOL; implants of long service in an organism have been defined for poly(methylphenylsiloxane). Non-inflammatory implantation of IOL, when the manufacturing of lenses is performed under spectral control at several stages, has been realized. New siloxane–polyurethane block copolymers promising for ophthalmology have been studied and passivated surfaces have been obtained.     

Vibrational spectroscopy of N-phenylmaleimide

A combination of infrared, Raman and inelastic neutron scattering (INS) spectroscopies with density functional theory (DFT) calculations is used to provide a complete assignment of the vibrational spectra of N-phenylmaleimide and N-(perdeuterophenyl)maleimide. DFT is shown to give very good results for the frequencies and atomic displacements in the modes. These are used to generate INS spectra which are excellent agreement with the observed. The calculated infrared and Raman spectra are much less reliable, although this may be more of a presentation problem than a real failing.     

Vibrational spectroscopy of stichtite

Raman spectroscopy complimented with infrared spectroscopy has been used to study the mineral stitchtite, a hydrotalcite of formula Mg6Cr2(CO3)(OH)16.4H2O. Two bands are observed at 1087 and 1067 cm(-1) with an intensity ratio of approximately 2.5/1 and are attributed to the symmetric stretching vibrations of the carbonate anion. The observation of two bands is attributed to two species of carbonate in the interlayer, namely weakly hydrogen bonded and strongly hydrogen bonded. Two infrared bands are found at 1457 and 1381 cm(-1) and are assigned to the antisymmetric stretching modes. These bands were not observed in the Raman spectrum. Two infrared bands are observed at 744 and 685 cm(-1) and are assigned to the nu4 bending modes. Two Raman bands were observed at 539 and 531 cm(-1) attributed to the nu2 bending modes. Importantly the band positions of the paragenically related hydrotalcites stitchtite, iowaite, pyroaurite and reevesite all of which contain the carbonate anion occur at different wavenumbers. Consequently, Raman spectroscopy can be used to distinguish these minerals, particularly in the field where many of these hydrotalcites occur simultaneously in ore zones.     

Vibrational emission analysis of the CN molecules in laser-induced breakdown spectroscopy of organic compounds

Laser-induced breakdown spectroscopy (LIBS) of organic materials is based on the analysis of atomic and ionic emission lines and on a few molecular bands, the most important being the CN violet system and the C₂ Swan system. This paper is focused in molecular emission of LIBS plasmas based on the CN (B²Σ–X²Σ) band, one of the strongest emissions appearing in all carbon materials when analyzed in air atmosphere. An analysis of this band with sufficient spectral resolution provides a great deal of information on the molecule, which has revealed that valuable information can be obtained from the plume chemistry and dynamics affecting the excitation mechanisms of the molecules. The vibrational emission of this molecular band has been investigated to establish the dependence of this emission on the molecular structure of the materials. The paper shows that excitation/emission phenomena of molecular species observed in the plume depend strongly on the time interval selected and on the irradiance deposited on the sample surface. Precise time resolved LIBS measurements are needed for the observation of distinctive CN emission. For the organic compounds studied, larger differences in the behavior of the vibrational emission occur at early stages after plasma ignition. Since molecular emission is generally more complex than that involving atomic emission, local plasma conditions as well as plume chemistry may induce changes in vibrational emission of molecules. As a consequence, alterations in the distribution of the emissions occur in terms of relative intensities, being sensitive to the molecular structure of every single material.     

Vibrational spectroscopy of ion-irradiated ices

In the last 20 years we have studied some effects induced by fast ions (E approximately keV-MeV) impinging on solid materials (mainly ices) with a view to their astrophysical relevance. The main techniques used have been infrared and Raman spectroscopy. Here we review some of the results obtained so far concerning, in particular, the formation of new species not present in the original sample. When hydrocarbons are an important constituent of the target ion irradiation gives rise also to a refractory residue which is left over after warming up. In addition we present some preliminary results of a new study, still in progress, on the infrared properties of the organic residue formed after irradiation of an icy mixture with H-, C-, N- and O-bearing species. Furthermore we present the micro-Raman spectra of some fragments of Orgueil a carbonaceous chondrite meteorite. Some astrophysical applications of these laboratory results are also discussed.     

Vibrational spectroscopy of formamide-intercalated kaolinites

The vibrational spectroscopy of low and high defect kaolinites fully and partially intercalated with formamide have been determined using a combination of X-ray diffraction, DRIFT and Raman spectroscopy. Expansion of the high defect kaolinite to 10.09 A resulted in a decrease in the peak width of the d(001) peak attributed to a decrease in defect structures upon intercalation. Changes in the defect structures of the low defect kaolinite were observed. Additional infrared bands were observed for the formamide intercalated kaolinites at 3629 and 3606 cm(-1). The 3629 cm(-1) band is attributed to the hydroxyl stretching frequency of the inner surface hydroxyl group hydrogen bonded to the carboxyl group of the formamide. The 3606 cm(-1) band is ascribed to water in the interlayer. Concomitant changes are observed in both the hydroxyl deformation modes and in the carboxyl bands.     

Vibrational spectroscopy of acid treated vermiculites

The natural vermiculites from different localities (Bulgaria, Brazil, and South Africa) after acid treatment were used for this study. Differently acidified vermiculite samples were prepared from the natural vermiculite sample using different concentrations of hydrochloric acid (0.5 M and 1 M) and different reaction time (2 h and 4 h) at 80 °C. Natural vermiculites and acid treated vermiculites were analyzed by elemental analysis, X-ray diffraction (XRD) analysis and studied using Fourier transform infrared (FTIR) spectroscopy and dispersive Raman spectroscopy. According to the XRD analysis vermiculites are interstratified structures created in the different two-one-zero sheet hydrated phases. Ratio of intensities of spectrally deconvoluted bands at 1075 cm⁻¹ and 1000 cm⁻¹ (stretching vibration of SiO bonds of vermiculites and stretching vibration of SiO bonds of amorphous silica, respectively) was used to determine the content of amorphous silica in acid treated vermiculite samples. Study of the infrared and Raman spectra of the acidified vermiculites enable a comparison of these two spectroscopic data that have not yet been performed.     

Vibrational spectroscopy standoff detection of explosives

Standoff infrared and Raman spectroscopy (SIRS and SRS) detection systems were designed from commercial instrumentation and successfully tested in remote detection of high explosives (HE). The SIRS system was configured by coupling a Fourier-transform infrared interferometer to a gold mirror and detector. The SRS instrument was built by fiber coupling a spectrograph to a reflective telescope. HE samples were detected on stainless steel surfaces as thin films (2–30 μg/cm²) for SIRS experiments and as particles (3–85 mg) for SRS measurements. Nitroaromatic HEs: TNT, DNT, RDX, C4, and Semtex-H and TATP cyclic peroxide homemade explosive were used as targets. For the SIRS experiments, samples were placed at increasing distances and an infrared beam was reflected from the stainless steel surfaces coated with the target chemicals at an angle of ∼180° from surface normal. Stainless steel plates containing TNT and RDX were first characterized for coverage distribution and surface concentration by reflection–absorption infrared spectroscopy. Targets were then placed at the standoff distance and SIRS spectra were collected in active reflectance mode. Limits of detection (LOD) were determined for all distances measured for the target HE. LOD values of 18 and 20 μg/cm² were obtained for TNT and RDX, respectively, for the SIR longest standoff distance measured. For SRS experiments, as low as 3 mg of TNT and RDX were detected at 7 m source–target distance employing 488 and 514.5 nm excitation wavelengths. The first detection and quantification study of the important formulation C4 is reported. Detection limits as function of laser powers and acquisition times and at a standoff distance of 7 m were obtained.     

Vibrational spectroscopy of mechanically compressed monolayers

Sum-frequency spectroscopy has been used to investigate the behavior of self-assembled monolayers in a solid-solid contact. Various alkanethiol layers on gold were observed before, during, and after compression to 660 MPa against a sapphire counterface. Well-ordered layers that differ only in the length of their alkane tails (C(8) versus C(18)) behave similarly. In contrast, defective and partly melted monolayers are more sensitive to stress than are their well-ordered analogues, and they are more prone to irreversible changes. In all cases, the intensity of methyl C-H stretching modes decreases with applied pressure, indicating a loss of net orientational order among the terminal methyl groups. The magnitude of this effect in well-ordered layers can be compared with the theoretical sensitivity of the resonant sum-frequency signal to molecular orientation. On these grounds, an increased population of terminal gauche conformers is identified as the disordering mechanism under pressure.     

Vibrational overtone spectroscopy of three-membered rings

We have recorded vapor-phase photoacoustic spectra of cyclopropane, ethylene oxide, and ethylene sulfide in the third, fourth, and fifth CH-stretching overtone regions. We have used a harmonically coupled anharmonic oscillator local mode model to facilitate analysis of the spectra. Fermi resonance between the CH-stretching and HCH-bending vibrations is essential to explain the observed wide and multistructured CH-stretching overtone bands. A number of weak combination bands can account for the remaining experimental features observed to the blue of the CH-stretching regions. We have reassigned the fundamental spectra of these three-membered rings.     

Poly(m-phenylene disulfide): Antimony pentafluoride doping and infrared spectroscopy

Poly(m-phenylene disulfide) treated with SbF₅ gives an unstable blue-black material. Heating of doped samples at 155°C leads to some stabilization to ambient conditions; doped and heated pellets exhibit a conductivity of 10^?9 and 10^?5 S/cm for vapor and liquid doping, respectively. To investigate backbone modifications, polymer powders have been treated with large amounts of liquid SbF₅ and an analysis of the IR spectra of the extracted samples has been tried in comparison with that of pristine polymer. Evidence for SbF ion has been found in the IR spectra of the complexes.     

Vibrational spectroscopy of solids under high pressures. Part I. Raman spectra of inorganic hexafluorometallate compounds

Raman spectra of a series of isomorphous hexafluorometallates (TlSbF₆; BaMF₆, M = Si, Ge, Sn, and Ti, space group $\text{R}\text{3}\text{m-D}{}^5{}_{\mathrm{3d}}\text{, Z = 1}$) have been measured under high pressures up to 25 kbar with a new opposed sapphire anvil cell. Pressure calibration has been achieved by means of the R₁ fluorescence band of ruby. The frequency of the only Raman active lattice mode (libration of the octahedral anion) of each compound shows a higher pressure dependence than do the internal vibrations of the anions. The E_g components of the ν₅ modes of the MF₆ octahedra which are coupled to the E_g lattice modes because of their same symmetries and small frequency differences exhibit higher pressure sensitivities than do the uncoupled internal modes. These findings may be used as a further means for symmetry assignment. BaGeF₆ undergoes a reversible phase transition at 9.6 kbar; the split librational modes of the high-pressure phase show the highest pressure dependences of up to about 3 cm^?1 · kbar^?1 found in this investigation.