Fourier transform infrared synchrotron ellipsometry for studying the anisotropy of small organic samples.

An experimental setup for polarization-dependent and spectroscopic ellipsometric measurements was developed that utilizes the brilliance of synchrotron infrared radiation at the electron storage ring at BESSY II for investigations of small samples and sample areas. During commissioning of the beamline and the experimental setup, a 1 mm2 piece of a well-characterized polyimide film was studied to show the benefits of Fourier transform infrared (FT-IR) synchrotron ellipsometry. The band shapes are interpreted with respect to the anisotropic distribution of transition dipole moments within the film. In comparison to a globar source, the signal intensity has been improved by more than one order of magnitude for this example.

Vibrational analysis of 2-[4-(N-dodecanoylamino)phenyl]-5-(4-nitrophenyl)-1,3,4-oxadiazole.

The infrared absorption spectra of 2-[4-( N -dodecanoylamino)phenyl]-5-(4-nitrophenyl)-1,3,4-oxadiazole (also denoted AF51) in solution and in the solid state as well as the solid-state Raman spectrum of the powdered compound are compared with the infrared linear dichroic (LD) spectra recorded at two orthogonal polarizations. The IR-LD spectra were measured in an anisotropic solvent-the nematic liquid crystal ZLI-1695 (Merck). The solvent spectrum taken under precisely the same experimental conditions and polarized radiation azimuths was subtracted from the polarized sample spectra in order to achieve pure oriented spectra of the compound studied. These spectra were further processed using a stepwise reduction procedure that allows for assignment of vibrational modes having mutually orthogonal dipole moments.

Instrumentation for FT-IR reflection spectroscopy with synchrotron radiation.

A versatile experimental set-up for infrared reflectance measurements with synchrotron radiation and its adaptation to a beamline is presented. Particular consideration is given to the collimation and the polarization of incident radiation. The performance is characterized with experimental results. Due to the high brilliance of the synchrotron radiation source, the irradiation of samples smaller than 1 mm(2) was found to be improved by more than one order of magnitude when compared to a globar.

Infrared ellipsometric view on monolayers: towards resolving structural details.

The optical constants in the infrared spectral range and the thickness of a surface layer are simultaneously determined by reflection based spectroscopic infrared ellipsometry. In the past experimental progress has been used to increase sensitivity with the aim to detect ever thinner layers. Reaching the monolayer limit by now, methodic efforts focus on revealing structural details such as anisotropy and lateral heterogeneity caused primarily by molecular orientational order. The basis of the method and present methodical approaches are outlined. Aspects of using synchrotron radiation for infrared ellipsometry and of setting up an infrared beamline are discussed.

Development of a simple gradient LC-IR interface for the detection of terpenoids from the alpha-pinene-ozone reaction.

The development of a simple interface between liquid chromatography and infrared spectroscopy (LC-IR) using a coaxial sprayer is described for less volatile analytes. The system consists of a transfer capillary, in which the analytes are transported from the separation column of the gradient-LC to the outlet of the sprayer. This transfer capillary is coaxially surrounded at the outlet by a stainless steel sprayer capillary, which is resistively heated and flushed with nitrogen gas. The samples are sprayed in the manner that the eluent is vaporized by the heated nitrogen when exiting the capillary, while the analytes are deposited on a moving slide made of infrared transparent material (ZnSe or CaF2). Afterwards the deposited compounds are analyzed with an infrared microscope in transmission. First results from reaction products of the gas phase reaction of alpha-pinene with ozone are presented.

Degradation of alpha-pinene on Tenax during sample storage: effects of daylight radiation and temperature.

The behavior of alpha-pinene sampled on adsorption cartridges filled with Tenax TA has been investigated in relation to different storage conditions, focusing on daylight radiation and temperature. After sampling, the respective cartridges containing the terpene were placed in sunlight on the windowsill for up to 1 month. Corresponding samples have been wrapped in aluminum foil to prevent the influence of daylight radiation. Additional sample cartridges with alpha-pinene were stored in the refrigerator at 4 degrees C and a freezer at -18 degrees C. All cartridges were analyzed using thermodesorption injection onto a gas chromatograph, and the compounds were detected using either a cryocondensation-interface to a Fourier transform infrared-spectrometer (GC/FT-IR) or the flame ionization detector (FID). In summary, 12 compounds were detected and identified, from which eight were products that were formed on Tenax through different mechanisms. Two compounds seemed to be formed under the influence of daylight radiation, while the others appear to be mainly autoxidation products. Estimates after 1 month of storage showed recoveries of over 99% for wrapped samples, while for unwrapped cartridges only about 88% of alpha-pinene was found. A pattern of up to five compounds was found that can be used as an indicator for storage reactions.

Ellipsometric studies related to surface-enhanced infrared absorption.

Infrared ellipsometry has been applied to determine the refractive index n and the absorption index k as well as the thickness of metal island films causing surface enhanced infrared absorption (SEIRA). The results from numerous films prepared in several campaigns are presented. For films of a nominal thickness of 6 nm, k is found to range from 0 to 3, while n ranges from 5 to 8. Among these two optical constants a close correlation is observed. Layers suitable for SEIRA exhibit an unusual spectral feature whose origin is explained.

Application of gas chromatography-cryocondensation-Fourier transform infrared spectroscopy and gas chromatography-mass spectrometry to the identification of gas phase reaction products from the alpha-pinene/ozone reaction.

The gas phase reaction of alpha-pinene with the atmospheric oxidant ozone was investigated by using the capabilities of both gas chromatography-cryocondensation-Fourier transform infrared spectroscopy (GC-FT-IR) and gas chromatography-mass spectrometry (GC-MS), for the identification of the reaction products formed. The reaction was carried out in a flow reaction chamber from where the compounds were sampled on Tenax-containing adsorption cartridges. The reaction mixture was injected onto the column after thermodesorption and analyzed using both GC-IR and GC-MS. Twenty compounds could be detected, including the reactant alpha-pinene and it's impurities tricyclene and camphene. Eleven compounds were identified by spectra comparison with either reference data or spectra obtained from commercial standards. Four compounds were tentatively identified from their IR and MS spectra, while from the remaining two compounds the nature of basic functional groups could be established.