ABSTRACT
The two enantiomers of 2,2'-bioxirane were synthesized, and their chiroptical properties were thoroughly investigated in various solvents by polarimetry, vibrational circular dichroism (VCD), and Raman optical activity (ROA). Density functional theory (DFT) calculations at the B3LYP/aug-cc-pVTZ level revealed the presence of three conformers (G+ , G- , and cis) with Gibbs populations of 51, 44, and 5% for the isolated molecule, respectively. The population ratios of the two main conformers were modified for solvents exhibiting higher dielectric constants (G- form decreases whereas G+ form increases). The behavior of the specific optical rotation values with the different solvents was correctly reproduced by time-dependent DFT calculations using the polarizable continuum model (PCM), except for the benzene for which explicit solvent model should be necessary. Finally, VCD and ROA spectra were perfectly reproduced by the DFT/PCM calculations for the Boltzmann-averaged G+ and G- conformers.
ABSTRACT
We investigated the fine structure of a self-assembled monolayer of dodecanethiol functionalized by alpha-quaterthiophene on gold (alpha-4TC 12H 24SH). The molecular orientation, quantified using polarization modulation infrared reflection-absorption spectroscopy, was studied as a function of the adsorption time. The alpha-4T moieties arrange in the upright position on the surface as the adsorption time increases, while the alkyl chain organization remains poor. Here we quantify the orientation of the self-assembled monolayer and, more significantly, reveal through surface X-ray diffraction that after a long incubation period (12 h) the alpha-4T on the gold surface adopts a 2D crystal structure.
ABSTRACT
In this paper, we present a simple way to increase the sensitivity of polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS) for the study of ultrathin films deposited on dielectric and semiconductor substrates. The enhancement of the absorption band intensity is obtained by reducing the signal arising from the substrate. This is achieved by adding a polarizer after the sample in order to balance the polarized reflectivities of the sample. As a consequence, the contribution of the film to the PM-IRRAS signal is increased relative to that of the substrate. An enhancement factor of about 10 has been obtained for ultrathin organic films deposited on glass and spread at the air-water interface. This method has also allowed the study of the very thin native oxide layer present on silicon without the need for the reference spectrum of bare silicon.
Subject(s)
Spectroscopy, Fourier Transform Infrared/methods , Semiconductors , Sensitivity and Specificity , Surface PropertiesABSTRACT
O-K edge XANES spectroscopy evidences structural modification induced by thermal poling treatment in surfaces of bulk Herasil silica glass presenting second harmonic generation. Considering model silicon dioxide clusters, calculations based on full multiple scattering approach have been performed in order to explain accurately the differences observed on XANES spectra at different stage of the poling treatment. These structural modifications on extreme surface affect both network and defects by breaking Si-O-Si bridging bonds. Despite of the formation of bridging bond occurring during the thermal depoling -which erases the SHG inside the glass-, the initial structure of the unpoled sample is not reproduced.
ABSTRACT
Quantitative orientation measurements by attenuated total reflectance (ATR) infrared spectroscopy require the accurate knowledge of the dichroic ratio and of the mean-square electric fields along the three axes of the ATR crystal. In this paper, polarized ATR spectra of single supported bilayers of the phospholipid dimyristoylphosphatidic acid covered by either air or water have been recorded and the dichroic ratio of the bands due to the methylene stretching vibrations has been calculated. The mean-square electric field amplitudes were calculated using three formalisms, namely the Harrick thin film approximation, the two-phase approximation, and the thickness- and absorption-dependent one. The results show that for dry bilayers, the acyl chain tilt angle varies with the formalism used, while no significant variations are observed for the hydrated bilayers. To test the validity of the different formalisms, s- and p-polarized ATR spectra of a 40-A lipid layer were simulated for different acyl chain tilt angles. The results show that the thickness- and absorption-dependent formalism using the mean values of the electric fields over the film thickness gives the most accurate values of acyl chain tilt angle in dry lipid films. However, for lipid monolayers or bilayers, the tilt angle can be determined with an acceptable accuracy using the Harrick thin film approximation. Finally, this study shows clearly that the uncertainty on the determination of the tilt angle comes mostly from the experimental error on the dichroic ratio and from the knowledge of the refractive index.
