An infrared study on Langmuir-Blodgett films of octadecylammonium octadecanoate: FWHM and the vibrational coupling

The monolayer of the mixture of octadecanoic acid and octadecylamine with molar ratio 1: 1 has been investigated at the air-water interface. It was found that the monolayer shows a rather stable state at the surface pressure of 30 mN/m and this monolayer can be transferred onto a CaF2 plate by Langmuir-Blodgett (LB) technique. The infrared spectra of LB films indicated that octadecyl ammonium octadecanoate is formed by an intermolecular proton exchange between adjacent carboxylic and aminic groups (COO- and NH3+). In three-layer LB film, the CH2 scissoring mode of the long hydrocarbon chains of octadecyl ammonium octadecanoate shows a broad band feature at about 1468 cm(-1) while this vibrational mode of three-layer LB film of the mixture (1: 1) of deuterated stearic acid and octadecylamine (octadecylammonium octadecanoate-d35, C18H37NH3+C17D35COO-) only shows a narrow band. The broad feature of the CH2 scissoring mode in octadecylammonium octadecanoate probably originates from the coupling between the chain of stearic acid and that of octadecylamine while this kind of coupling could be completely removed in octadecylammonium octadecanoate-d35.

AN INFRARED SPECTROSCOPIC STUDY ON THE STRUCTURAL PHASE-TRANSITIONS OF LAURYLAMMONIUM CHLORIDE

Infrared spectroscopy was used to study the structural phase, transitions of laurylammonium chloride in the temperature range from 290 to 365K. It was shown that there is a solid-solid phase transition at 339 K with a pre-transition at 327 K. The infrared spectra indicated that virgin crystals at room temperature form a well-ordered phase with all-trans hydrocarbon chains, and the lengths of N-H...Cl hydrogen bonds are different. The spectra suggested that the gauche conformers begin to appear at temperature above 327 K. The spectra at high temperature over 339 K demonstrated that the interaction between the chains decreases, the partial ''melting'' of the chains is obvious, and the hydrogen bonds (N-H...Cl) have the same lengths. The main transition and pre-transition are mainly assigned to the intramolecular and intermolecular order-disorder changes, respectively.

AN INFRARED SPECTROSCOPIC CHARACTERIZATION OF THE SOLID SOLID BEHAVIOR OF DODECYLAMMONIUM CHLORIDE

The infrared spectra of the bilayer system dodecylammonium chloride has been studied as a function of temperature. Unusual splitting of some vibrational modes helps us to characterize the structure of different solid states. This study provided the evidence for the occurrence of an order-disorder phase transition whose onset occurs at 327 K and its completion ends at 339 K. In the low temperature phase below 327 K, the virgin crystals form a well-ordered phase with all-transhydrocarbon chains. In the intermediate state between 327 and 339 K, the data demonstrate the introduction of intramolecular as well as intermolecular disorder. The coexistence of solid and liquid-crystal-like states is shown by the persistence of factor group splittings together with the existence of defect bands in the wide intermediate temperature range. In the high temperature phase over 339 K the crystals convert to a liquid-crystal-like system with extensive motional and conformational disorder, but still show characteristics in their infrared spectra which indicate the presence of ordered segments in the hexagonal solid phase.

AN INFRARED SPECTROSCOPIC STUDY OF THE STRUCTURAL PHASE-TRANSITION IN THE PEROVSKITE-TYPE LAYER COMPOUND [N-C16H33NH3]2COCL4

The solid-solid phase transitions in the perovskite-type layer compound [n- C16H33NH3]2CoCl4 have been studied by infrared spectroscopy. A new phase transition at 340 K was found by comparison with differential scanning calorimetry results. A temperature dependence study of the infrared spectra provides evidence of the occurrence of structural phase transitions related to the dynamics of the alkylammonium ions and hydrogen bonds. The main transition at 374 K corresponds to the conformational order-disorder change in the chain, which probably couples with reorientational motions of the NH3 polar heads. GTG or GTG' defects appear in the high temperature disordered phase.

Temperature dependence of the mid-infrared dielectric function of YBCO in the ab plane

We have excited mid-infrared surface plasmons in two YBCO thin films of contrasting properties using attenuated total reflection of light and found that the imaginary part of the dielectric function decreases linearly with reduction in temperature. This result is in contrast with the commonly reported conclusion of infrared normal reflectance studies. If sustained it may clarify the problem of understanding the normal state properties of YBCO and the other cuprates. The dielectric function of the films, epsilon = epsilon(1) + i epsilon(2), was determined between room temperature and 80K: epsilon(1) was found to be only slightly temperature dependent but somewhat sample dependent, probably as a result of surface and grain boundary contamination. The imaginary part, epsilon(2), (and the real part of the conductivity, sigma(1),) decreased linearly with reduction in temperature in both films. Results obtained were: for film 1: epsilon(1) = - 14.05 - 0.0024T and epsilon(2) - 4.11 + 0.086T and for film 2: epsilon(1) = - 24.09 + 0.0013T and epsilon(2) = 7.66 + 0.067T where T is the temperature in Kelvin. An understanding of the results is offered in terms of temperature-dependent intrinsic intragrain inelastic scattering and temperature-independent contributions: elastic and inelastic grain boundary scattering and optical interband (or localised charge) absorption. The relative contribution of each is estimated. A key conclusion is that the interband (or localised charge) absorption is only similar to 10%. Most importantly, the intrinsic scattering rate, 1/tau, decreases linearly with fall in temperature, T, in a regime where current theory predicts dependence on frequency, omega, to dominate. The coupling constant, lambda, between the charge carriers and the thermal excitations has a value of 1.7, some fivefold greater than the far infrared value. These results imply a need to restate the phenomenology of the normal state of high temperature superconductors and seek a corresponding theoretical understanding.

A Stubbornly Large Mass of Cold Dust in the Ejecta of Supernova 1987A

We present new Herschel photometric and spectroscopic observations of Supernova 1987A, carried out in 2012. Our dedicated photometric measurements provide new 70 mu m data and improved imaging quality at 100 and 160 mu m compared to previous observations in 2010. Our Herschel spectra show only weak CO line emission, and provide an upper limit for the 63 mu m [O-I] line flux, eliminating the possibility that line contaminations distort the previously estimated dustmass. The far-infrared spectral energy distribution (SED) is well fitted by thermal emission from cold dust. The newly measured 70 mu m flux constrains the dust temperature, limiting it to nearly a single temperature. The far-infrared emission can be fitted by 0.5 +/- 0.1M(circle dot) of amorphous carbon, about a factor of two larger than the current nucleosynthetic mass prediction for carbon. The observation of SiO molecules at early and late phases suggests that silicates may also have formed and we could fit the SED with a combination of 0.3M(circle dot) of amorphous carbon and 0.5M(circle dot) of silicates, totalling 0.8M(circle dot) of dust. Our analysis thus supports the presence of a large dust reservoir in the ejecta of SN 1987A. The inferred dust mass suggests that supernovae can be an important source of dust in the interstellar medium, from local to high-redshift galaxies.

Study of sewage sludge aimed at agricultural soil amendment by thermogravimetric analysis and fourier-transform infrared spectroscopy

Thermal degradation and gaseous products evolving from the pyrolysis of sewage sludge, aimed at agricultural soil amendment, were investigated using Thermogravimetric Analysis in conjunction with Fourier Transform Infrared Analysis (TG-FTIR). The materials were studied in temperatures ranging from 30 to 800 ºC. Furthermore infrared spectra of sewage sludge samples were performed as a complementary technique. In parallel the sewage sludge was spiked with ibuprofen in order to test whether the mentioned techniques are able to detect the drug. Thermal analysis showed the range of 200-400ºC as the most characteristic for weight loss, corresponding with the organic matter volatilization, while the range of 500-800ºC was also characteristic and due to the volatilization of carbonates. On the other hand, ibuprofen-spiking tests identified at temperature range (150-250ºC) where the compound totally volatilizes, therefore, in this work, the detection of ibuprofen by TGA was established for concentrations higher than 0.5 g/kg sludge, concentration 102 times higher than the concentrations measured by other authors in regular sewage sludge (Martín, et al., 2010). A correlation has been found between the ibuprofen concentrations in the sludge and the intensity of the absorption bands, both for FT-IR spectra at the maximum emission temperature for ibuprofen (232ºC) as for the FT-IR spectra of the non-pyrolyzed samples.

Optical properties of organic superconductor K-(BETS)2FeBr4 /

/c-(BETS)2FeBr4 is the first antiferromagnetic organic superconductor with successive antiferromagnetic and superconducting transitions at Ta^=2.5K and Tc=l.lK respectively at ambient pressure. Polarized reflectance measurements were performed on three single crystalsamples of this material using a Briiker IFS66V/S Interferometer, and a Bolometer detector or an MCT detector, at seven temperatures between 4K and 300K, in both the far-infrared and mid-infrared frequency range. After the reflectance results were obtained, the Kramers-Kronig dispersion relation was apphed to determine the optical conductivity of /c-(BETS)2FeBr4 at these seven temperatures. Additionally, the optical conductivity spectra were fitted with a Drude/Lorentz Oscillator model in order to study the evolution of the optical conductivity with temperature along the a-axis and c-axis. The resistivities calculated from the Drude model parameters along the a-axis and c-axis agreed reasonably with previous transport measurements.

Coriolis effects in symmetric top spectra /

The "x-y Coriolis Coupling Theory" as presented by Dilauro and Mills (1966) is reformulated and extended to the determination of Raman intensities. Theoretical Raman and Infrared spectra are computed in order to understand the effects due to this coupling in both types of spectra. Both the Infrared and Raman spectra obtained indicate very real effects due to Coriolis coupling. In some of the cases chosen the computed spectra are grossly different from the normal spectra where coupling is absent. Such large effects can greatly impede the interpretation of experimental results. Theoretical spectra therefore aids in the interpretation of experimental results, as is clearly demonstrated in the results of this work.

Crystal growth, Raman scattering and optical properties of the superconductor Cd2Re2O7(16O, 18O)/

Using the Physical Vapor Transport method, single crystals of Cd2Re207 have been grown, and crystals of dimensions up to 8x6x2 mm have been achieved. X-ray diffraction from a single crystal of Cd2Re207 has showed the crystal growth in the (111) plane. Powder X-ray diffraction measurements were performed on ^^O and ^^O samples, however no difference was observed. Assigning the space group Fd3m to Cd2Re207 at room temperature and using structure factor analysis, the powder X-ray diffraction pattern of the sample was explained through systematic reflection absences. The temperatiure dependence of the resistivity measurement of ^^O has revealed two structural phase transitions at 120 and 200 K, and the superconducting transition at 1.0 K. Using Factor Group Analysis on three different structiures of Cd2Re207, the number of IR and Raman active phonon modes close to the Brillouin zone centre have been determined and the results have been compared to the temperature-dependence of the Raman shifts of ^^O and ^*0 samples. After scaling (via removing Bose-Einstein and Rayleigh scattering factors from the scattered light) all spectra, each spectrum was fitted with a number of Lorentzian peaks. The temperature-dependence of the FWHM and Raman shift of mode Eg, shows the effects of the two structurjil phase transitions above Tc. The absolute reflectance of Cd2Re207 - '^O single crystals in the far-infrared spectral region (7-700 cm~^) has been measured in the superconducting state (0.5 K), right above the superconducting state (1.5 K), and in the normal state (4.2 K). Thermal reflectance of the sample at 0.5 K and 1.5 K indicates a strong absorption feature close to 10 cm~^ in the superconducting state with a reference temperature of 4.2 K. By means of Kramers-Kronig analysis, the absolute reflectance was used to calculate the optical conductivity and dielectric function. The real part of optical conductivity shows five distinct active phonon modes at 44, 200, 300, 375, and 575 cm~' at all temperatures including a Drude-like behavior at low frequencies. The imaginary part of the calculated dielectric function indicates a mode softening of the mode 44 cm~' below Tc.

Set-up and evaluation of a mid-infrared reflectometer and investigation of the optical properties of doped tin telluride

A system comprised of a Bomem interferometer and a LT3-110 Heli-Tran cryostat was set up to measure the reflectance of materials in the mid-infrared spectral region. Several tests were conducted to ensure the consistency and reliability of the system. Silicon and Chromium, two materials with well known optical properties were measured to test the accuracy of the system, and the results were found to be in good agreement with the literature. Reflectance measurements on pure SnTe and several Pb and Mn-doped alloys were carried out. These materials were chosen because they exhibit a strong plasma edge in the mid infrared region. The optical conductivity and several related optical parameters were calculated from the measured reflectance. Very low temperature measurements were carried out in the far-infrared on Sn9SMn2Te, and the results are indicative of a spin glass phase at 0.8 K. Resistivity measurements were made at room temperature. The resistivity values were found, as expected, to decrease with increasing carrier concentration and to increase with increasing manganese concentration.

Infrared Spectroscopy of Gadolinium

Measurements of the optical reflectivity of the normal incident light along c-axis [0001] have been made on a Gadolinium single crystal, for temperatures between 50 K and room temperature just above the Curie temperature of Gd, which is 293 K. And covering the spectrum range between 100 -11000 cm-I . This work is the first study of Gd in the far infrared range. In fact it fills the gap below 0.2 eV which has never been measured before. Extreme attention was paid to the fact that Gadolinium is a very reactive metal with air. Thus, the sample was mechanically polished and carefully handled during the measurement. However, temperature dependent optical measurements have been made in the same frequency range for a sample of Gd2O3. For comparison, both samples of Gd and Gd2O3 were examined by X-Ray diffraction. XRD analysis showed that the sample was pure gadolinium and the oxide layer either does not exist, or is very thin. Furthermore, this fact was supported by the absence of any of Gd2O3 features in the Gd sample reflectivity. Kramers Kronig analysis was applied to extract the optical functions from the reflectance data. The optical conductivity shows a strong temperature dependence feature in the mid-infrared. This feature disappears completely at room temperature which supports a magnetic origin.

Studies on molecular structure and properties using microwave and infrared spectral data

The major objective of the thesis is essentially to evolve and apply certain computational procedures to evaluate the structure and properties of some simple polyatomic molecules making use of spectroscopic data available from the literature. It must be said that though there is dwindling interest in recent times in such analyses, there exists tremendous scope and utility for attempting such calculations as the precision and reliability of'experimental techniques in spectroscopy have increased vastly due to enormous sophistication of the instruments used for these measurements. In the present thesis an attempt is made to extract maximum amount of information regarding the geometrical structure and interatmic forces of simple molecules from the experimental data on microwave and infrared spectra of these molecules

Raman and infrared spectral analysis of thallium niobyl phosphates: Tl2NbO2PO4, Tl3NaNb4O9(PO4)2 and TlNbOP2O7

Raman and infrared spectra of Tl2NbO2PO4, Tl3NaNb4O9(PO4)2 and TlNbOP2O7 are reported. The observed bands are assigned in terms of vibrations of NbO6 octahedra and PO4 tetrahedra in the first two compounds and in terms of NbO6 octahedra and P2O7 4− anion in the third compound. The NbO6 octahedra in all the title compounds are found to be corner-shared and distorted. The higher wavenumber values of the ν1 (NbO6) mode and other stretching modes indicate that the NbO6 octahedra in them are distorted in the order TlNbOP2O7 > Tl2NbO2PO4 > Tl3NaNb4O9(PO4)2. The splitting of the ν3 (PO4) mode indicates that PO4 tetrahedra is distorted more in Tl2NbO2PO4 than in Tl3NaNb4O9(PO4)2. The symmetry of P2O7 4− anion in TlNbOP2O7 is lowered. Bands indicate that the P–O–P bridge in the above compound has a bent P–O–P bridge configuration

Mid-infrared filters for astronomical and remote sensing instrumentation

As improvements to the optical design of spectrometer and radiometer instruments evolve with advances in detector sensitivity, use of focal plane detector arrays and innovations in adaptive optics for large high altitude telescopes, interest in mid-infrared astronomy and remote sensing applications have been areas of progressive research in recent years. This research has promoted a number of developments in infrared coating performance, particularly by placing increased demands on the spectral imaging requirements of filters to precisely isolate radiation between discrete wavebands and improve photometric accuracy. The spectral design and construction of multilayer filters to accommodate these developments has subsequently been an area of challenging thin-film research, to achieve high spectral positioning accuracy, environmental durability and aging stability at cryogenic temperatures, whilst maximizing the far-infrared performance. In this paper we examine the design and fabrication of interference filters in instruments that utilize the mid-infrared N-band (6-15 µm) and Q-band (16-28 µm) atmospheric windows, together with a rationale for the selection of materials, deposition process, spectral measurements and assessment of environmental durability performance.