Laser Spectroscopy: TDLAS instrumentation and NIR analysis of some organic materials

Near-infrared spectroscopy can be a workhorse technique for materials analysis in industries such as agriculture, pharmaceuticals, chemicals and polymers. A near-infrared spectrum represents combination bands and overtone bands that are harmonics of absorption frequencies in the mid-infrared. Near-infrared absorption includes a combination-band region immediately adjacent to the mid-infrared and three overtone regions. All four near-infrared regions contain "echoes" of the fundamental mid-infrared absorptions. For example, vibrations in the mid-infrared due to the C-H stretches will produce four distinct bands in each of the overtone and combination regions. As the bands become more removed from the fundamental frequencies they become more widely separated from their neighbors, more broadened and are dramatically reduced in intensity. Because near-infrared bands are much less intense, more of the sample can be used to produce a spectra and with near-infrared, sample preparation activities are greatly reduced or eliminated so more of the sample can be utilized. In addition, long path lengths and the ability to sample through glass in the near-infrared allows samples to be measured in common media such as culture tubes, cuvettes and reaction bottles. This is unlike mid-infrared where very small amounts of a sample produce a strong spectrum; thus sample preparation techniques must be employed to limit the amount of the sample that interacts with the beam. In the present work we describe the successful the fabrication and calibration of a linear high resolution linear spectrometer using tunable diode laser and a 36 m path length cell and meuurement of a highly resolved structure of OH group in methanol in the transition region A v =3. We then analyse the NIR spectrum of certain aromatic molecules and study the substituent effects using local mode theory

Hyperfine structure and isotopic shift of the n^2 P_J levels (n = 7-10) of ^203,205 TI measured by Doppler-free two-photon spectroscopy

Using Doppler-free two-photon absorption spectroscopy, we have measured hyperfine splitting constants as well as isotopic level shifts of the 6s^2 np ^2 P_l/2,3/2 states in (n=7-10) in ^203 TI and ^205 TI. Calculations for hyperfine constants and electron density at the nucleus have been performed by the Dirac-Fock method. The experimental results are compared with these calculations as well as with the predictions of the semiempirical theory.

Higher oxides of chlorine: absorption cross-sections of Cl2O6 and Cl2O4, the decomposition of Cl2O6, and the reactions of OClO with O and O-3

The absorption cross-sections of Cl2O6 and Cl2O4 have been obtained using a fast flow reactor with a diode array spectrometer (DAS) detection system. The absorption cross-sections at the wavelengths of maximum absorption (lambda(max)) determined in this study are those of Cl2O6: (1.47 +/- 0.15) x 10(-17) cm(2) molecule(-1), at lambda(max) = 276 nm and T = 298 K; and Cl2O4: (9.0 +/- 2.0) x 10(-19) cm(2) molecule(-1), at lambda(max) = 234 nm and T = 298 K. Errors quoted are two standard deviations together with estimates of the systematic error. The shapes of the absorption spectra were obtained over the wavelength range 200-450 nm for Cl2O6 and 200-350 nm for Cl2O4, and were normalized to the absolute cross-sections obtained at lambda(max) for each oxide, and are presented at 1 nm intervals. These data are discussed in relation to previous measurements. The reaction of O with OCIO has been investigated with the objective of observing transient spectroscopic absorptions. A transient absorption was seen, and the possibility is explored of identifying the species with the elusive sym-ClO3 or ClO4, both of which have been characterized in matrices, but not in the gas-phase. The photolysis of OCIO was also re-examined, with emphasis being placed on the products of reaction. UV absorptions attributable to one of the isomers of the ClO dimer, chloryl chloride (ClClO2) were observed; some Cl2O4 was also found at long photolysis times, when much of the ClClO2 had itself been photolysed. We suggest that reports of Cl2O6 formation in previous studies could be a consequence of a mistaken identification. At low temperatures, the photolysis of OCIO leads to the formation of Cl2O3 as a result of the addition of the ClO primary product to OCIO. ClClO2 also appears to be one product of the reaction between O-3 and OCIO, especially when the reaction occurs under explosive conditions. We studied the kinetics of the non-explosive process using a stopped-flow technique, and suggest a value for the room-temperature rate coefficient of (4.6 +/- 0.9) x 10(-19) cm(3) molecule(-1) s(-1) (limit quoted is 2sigma random errors). The photochemical and thermal decomposition of Cl2O6 is described in this paper. For photolysis at k = 254 nm, the removal of Cl2O6 is not accompanied by the build up of any other strong absorber. The implications of the results are either that the photolysis of Cl2O6 produces Cl-2 directly, or that the initial photofragments are converted rapidly to Cl-2. In the thermal decomposition of Cl2O6, Cl2O4 was shown to be a product of reaction, although not necessarily the major one. The kinetics of decomposition were investigated using the stopped-flow technique. At relatively high [OCIO] present in the system, the decay kinetics obeyed a first-order law, with a limiting first-order rate coefficient of 0.002 s(-1). (C) 2004 Elsevier B.V. All rights reserved.

Cavity-enhanced absorption: detection of nitrogen dioxide and iodine monoxide using a violet laser diode

We present an application of cavity-enhanced absorption spectroscopy with an off-axis alignment of the cavity formed by two spherical mirrors and with time integration of the cavity-output intensity for detection of nitrogen dioxide (NO2) and iodine monoxide (IO) radicals using a violet laser diode at lambda = 404.278 nm. A noise-equivalent (1sigma = root-mean-square variation of the signal) fractional absorption for one optical pass of 4.5x10(-8) was demonstrated with a mirror reflectivity of similar to0.99925, a cavity length of 0.22 m and a lock-in-amplifier time constant of 3 s. Noise-equivalent detection sensitivities towards nitrogen dioxide of 1.8x10(10) molecule cm(-3) and towards the IO radical of 3.3x10(9) molecule cm(-3) were achieved in flow tubes with an inner diameter of 4 cm for a lock-in-amplifier time constant of 3 s. Alkyl peroxy radicals were detected using chemical titration with excess nitric oxide (RO2 + NO --> RO + NO2). Measurement of oxygen-atom concentrations was accomplished by determining the depletion of NO2 in the reaction NO2 + O --> NO + O-2. Noise-equivalent concentrations of alkyl peroxy radicals and oxygen atoms were 3x10(10) molecule cm(-3) in the discharge-flow-tube experiments.

Monitoring guanine photo-oxidation by enantiomerically resolved Ru(II) dipyridophenazine complexes using inosine-substituted oligonucleotides

The intercalating [Ru(TAP)2(dppz)]2+ complex can photo-oxidise guanine in DNA, although in mixed-sequence DNA it can be difficult to understand the precise mechanism due to uncertainties in where and how the complex is bound. Replacement of guanine with the less oxidisable inosine (I) base can be used to understand the mechanism of electron transfer (ET). Here the ET has been compared for both L- and D-enantiomers of [Ru(TAP)2(dppz)]2+ in a set of sequences where guanines in the readily oxidisable GG step in {TCGGCGCCGA}2 have been replaced with I. The ET has been monitored using picosecond and nanosecond transient absorption and ps-time-resolved IR spectroscopy. In both cases inosine replacement leads to a diminished yield, but the trends are strikingly different for L- and D-complexes.

Self-assembling of phenothiazine compounds investigated by small-angle X-ray scattering and electron paramagnetic resonance spectroscopy

Small-angle X-ray scattering (SAXS) and electron paramagnetic resonance (EPR) have been carried out to investigate the structure of the self-aggregates of two phenothiazine drugs, chlorpromazine (CPZ) and trifluoperazine (TFP), in aqueous solution. In the SAXS studies, drug solutions of 20 and 60 mM, at pH 4.0 and 7.0, were investigated and the best data fittings were achieved assuming several different particle form factors with a homogeneous electron density distribution in respect to the water environment. Because of the limitation of scattering intensity in the q range above 0.15 angstrom(-1), precise determination of the aggregate shape was not possible and all of the tested models for ellipsoids, cylinders, or parallelepipeds fitted the experimental data equally well. The SAXS data allows inferring, however, that CPZ molecules might self-assemble in a basis set of an orthorhombic cell, remaining as nanocrystallites in solution. Such nanocrystals are composed of a small number of unit cells (up to 10, in c-direction), with CPZ aggregation numbers of 60-80. EPR spectra of 5- and 16-doxyl stearic acids bound to the aggregates were analyzed through simulation, and the dynamic and magnetic parameters were obtained. The phenothiazine concentration in EPR experiments was in the range of 5-60 mM. Critical aggregation concentration of TFP is lower than that for CPZ, consistent with a higher hydrophobicity of TFP. At acidic pH 4.0 a significant residual motion of the nitroxide relative to the aggregate is observed, and the EPR spectra and corresponding parameters are similar to those reported for aqueous surfactant micelles. However, at pH 6.5 a significant motional restriction is observed, and the nitroxide rotational correlation times correlate very well with those estimated for the whole aggregated particle from SAXS data. This implies that the aggregate is densely packed at this pH and that the nitroxide is tightly bound to it producing a strongly immobilized EPR spectrum. Besides that, at pH 6.5 the differences in motional restriction observed between 5- and 16-DSA are small, which is different from that observed for aqueous surfactant micelles.

SrZrO3 powders obtained by chemical method: Synthesis, characterization and optical absorption behaviour

Strontium zirconate (SrZrO3) powders have been synthesized by the polymeric precursor method after heat treatment at different temperatures for 2 h in oxygen atmosphere. The decomposition of precursor powder was followed by thermogravimetric analysis, X-ray diffraction (XRD) and Fourier transform Raman (FT-Raman). The UV-vis absorption spectroscopy measurements suggested the presence of intermediary energy levels in the band gap of structurally disordered powders. XRD, Rietveld refinement and FT-Raman revealed that the powders are free of secondary phases and crystallizes in the orthorhombic structure. (C) 2007 Elsevier Masson SAS. All rights reserved.

Synthesis, characterization, structural refinement and optical absorption behavior of PbWO(4) powders

The present paper describes the synthesis, characterization, structural refinement and optical absorption behavior of lead tungstate (PbWO(4)) powders obtained by the complex polymerization method heat treated at different temperatures for 2h in air atmosphere. PbWO(4) powders were characterized by X-ray diffraction (XRD), Rietveld refinement, Fourier transform Raman (FT-Raman) spectroscopy and ultraviolet visible (UV-vis) absorption spectroscopy measurements. XRD, Rietveld refinement and FT-Raman revealed that PbWO(4) powders are free of secondary phases and crystallizes in a tetragonal structure. The UV-vis absorption spectroscopy measurements suggest the presence of intermediary energy levels into the band gap of structurally disordered powders. (C) 2008 Elsevier B.V. All rights reserved.

UV-visible absorption characteristics of TEOS-derived and Cr-doped silica sonogels aged in different pH solutions and heat treated up to 600 degrees C

Cr-doped xerogels were obtained by sol-gel process from the acid-catalyzed and ultrasound-stimulated hydrolysis of tetraethoxysilane (TEOS) with addition of CrCl3.6H(2)O in water solution during the liquid step of the process. The gels were aged immersed in different pH solutions for about 30 days, after that they were allowed to dry. The samples were annealed at temperatures ranging from 40 to 600degreesC and analyzed by UV-visible absorption spectroscopy. Cr3+ is the preferable oxidation state of the chromium ion in the gels annealed up to 250-300degreesC, in the case of aging in solutions of pH=5 and 11. A high UV absorption below similar to320 nm, due to the host gel, and different absorption bands, depending on the temperature, due to the chromium ion were observed in the xerogels at temperatures below similar to250degreesC, in the case of aging in solutions of pH=1 and 2. These absorption bands have not been assigned. Above 300degreesC up to 600degreesC, Cr5+, and possibly Cr6+, are the preferable oxidation states of the chromium ion independent of the pH of the aging solution, so the xerogels turn to a yellowish appearance in all cases.

EXAFS and Raman spectroscopy study of binary indium fluoride glasses

Extended X-ray absorption fine spectroscopy (EXAFS) and Raman scattering studies of InF3-BaF2 and InF3-SrF2 binary glasses are reported. For all compositions, the local structure of the glasses is built with InF6 units. For all glasses studied, the indium neighbour's number and the In-F mean bond length are equal to the values of the InF3 crystalline phase (6 and 0.205 nm, respectively). © 1996 Chapman & Hall.

High resolution spectroscopy of 13CH3OH around the 10R(20) CO2 laser emission: New FIR laser lines, frequency measurement and assignments

We investigated the IR absorption spectrum of 13CH3OH around the frequency of the 10R(20) CO2 laser line. We found two absorption lines which can be excited by 10R(20) and studied the FIR laser emissions excited by this pump line using a waveguide CO2 laser of 300 MHz tunability. We report two new FIR laser lines of large offset, not previously observed due to their weakness and closeness to other stronger lines. We measured the frequencies of five FIR laser lines for the first time by an accurate heterodyne technique and present the complete assignments of the IR-FIR laser systems relative to this pump line. Furthermore we present new frequency values for two FIR laser lines whose frequencies had been previously wrongly measured. Copyright © 1997 Elsevier Science Ltd.

Absorption and fluorescence of Er3+-doped LiYF4: Measurements and simulation

Er3+:LiYF4 single crystal has been studied by absorption and fluorescence spectroscopy in the IR-visible-UV (0-44000 cm-1) region from 4.2 K to room temperature. Polarized spectra were recorded in order to assign numerous Stark levels of electronic transitions mentioned but not attributed before in the related literature and to discuss the irreducible representations (irreps) of the 4I15/2 sublevels. A parametric hamiltonian, including free ion (Eν, α, β, γ, Tλ, ζ, Mk and Pi) and crystal field parameters (B2 0, B4 0, B4 4, B6 0 and B6 4) in an approximate D2d symmetry for the rare earth site in this scheelite type structure, was used to simulate 109 energy positions of the Er ion with a r.m.s. standard deviation of 14.6 cm-1. A comparison with previously published results for Nd3+ in the same matrix is done. © 1998 Elsevier Science S.A.

Giant non-linear absorption in Er3+-doped fluoroindate glass

Non-linear absorption is observed in Er3+-doped fluoroindate glass (in mol% 37InF2:20ZnF2:20SrF2:16BaF2:2GdF2: 2NaF:1GaF3:2ErF3) when the sample is irradiated with a CW laser emitting at 650 nm. An intensity dependence of the optical transmittance is detected. Saturation and sequential absorption of two photons are responsible for the decrease of 50% in the transmittance. The results are explained by simple models which are solved based on rate-equations for the populations of energy levels.

Determination of copper in fish feed by graphite furnace atomic absorption spectrometry using slurry sampling

The present work develops and optimizes a method to determine copper in samples of feces and fish feed by graphite furnace atomic absorption spectrometry (GFAAS) through the direct introduction of slurries of the samples into the spectrometer's graphite tube coated internally with metallic rhodium and tungsten carbide that acts as chemical modifiers. The limits of detection (LOD) and quantification (LOQ) calculated for 20 readings of the blank of the standard slurries (0.50% m/v of feces or feed devoid of copper) were 0.24 and 0.79 μg L -1 for the standard feces slurries and 0.26 and 0.87 μg L -1 for the standard feed slurries. The proposed method was applied in studies of absorption of copper in different fish feeds and their results proved compatible with that obtained from samples mineralized by acid digestion using microwave oven. © Springer Science+Business Media, LLC 2008.

Local order of Pb1-xLaxZr0.40Ti 0.60O3 ferroelectric ceramic materials probed by X-ray absorption and Raman spectroscopies

This paper reports on the structural characterization of Pb 1-xLaxZr0.40Ti0.60O3 (PLZT) ferroelectric ceramic compositions prepared by the conventional solid state reaction method. X-ray absorption spectroscopy (XAS) and Raman spectroscopy were used to probe the local structure of PLZT samples that exhibits a normal and relaxor ferroelectric behavior. From the Zr K-edge and Pb LIII-edge EXAFS spectra, a considerable dissymmetry of Zr and Pb sites was observed in all samples, including those showing a long-range order cubic symmetry and a relaxor behavior. The Raman spectroscopy results confirmed the existence of a local disorder in all PLZT samples through the observation of Raman active vibrational modes. The variation in the intensity of the E(TO 3) mode in the PLZT relaxor samples indicates that the process of correlation between nanodomains stabilizes at temperatures lower than T m. © 2013 Elsevier B.V. All rights reserved.