Solvation of Al3+ cations in bulk and confined protic ionic liquids: a computational study.

Despite the growing interest in the potential electrochemical applications of both aluminium and ionic liquids in batteries, the microstructure of mixtures of trivalent salts and these dense ionic environments is completely unknown. In this work, the solvation of Al3+ cations in highly dense ionic solvents is investigated. For this purpose, molecular dynamics simulations of mixtures of a protic ionic liquid, ethylammonium nitrate (EAN), with aluminium nitrate (Al(NO3)3), both in bulk and confined between graphene walls, are performed. Several structural quantities of the system are calculated for different salt concentrations, such as densities, radial distribution functions, structure factors, coordination numbers and hydrogen bonds for the bulk mixture and ionic density profiles for the confined ones. Moreover, vibrational density of states is calculated for the salt cations, both in bulk and when close to the walls. The results obtained are analyzed and compared to those for mixtures of EAN with monovalent and divalent salts, in order to probe the influence of the salt cation charge on the system's properties. Finally, ab initio density functional theory calculations were performed in order to analyze the structure of the Al3+-ligand complexes, and their predictions for the Raman spectrum are compared both to the corresponding experimental one and the one coming from molecular dynamics simulations. According to our calculations, [Al(NO3)6]3- octahedral complexes do not significantly change the microstructure of the mixtures relative to those of Mg2+-based ones.

Refractive index measurements in absorbing media with white light spectral interferometry.

White light spectral interferometry is applied to measure the refractive index in absorbing liquids in the spectral range of 400-1000 nm. We analyze the influence of absorption on the visibility of interferometric fringes and, accordingly, on the measurement of the refractive index. Further, we show that the refractive index in the absorption band can be retrieved by a two-step process. The procedure requires the use of two samples of different thickness, the thicker one to retrieve the refractive index in the transparent region and the thinnest to obtain the data in the absorption region. First, the refractive index values are retrieved with good accuracy in the transparent region of the material for 1-mm-thick samples. Second, these refractive index values serve also to precisely calculate the thickness of a thinner sample (~150 µm) since the accuracy of the methods depends strongly on the thickness of the sample. Finally, the refractive index is recovered for the entire spectral range.

Spectrally resolved white light interferometry to measure material dispersion over a wide spectral band in a single acquisition.

In this paper we apply spectrally resolved white light interferometry to measure refractive and group index over a wide spectral band from 400 to 1000 nm. The output of a Michelson interferometer is spectrally decomposed by a homemade prism spectrometer with a high resolution camera. The group index is determined directly from the phase extracted from the spectral interferogram while the refractive index is estimated once its value at a given wavelength is known.

Schwarzschild spectrometer.

This is a proposal and description of a new spectrometer based on the Schwarzschild optical system. The proposed design contains two Schwarzschild optical systems. Light diverging from the spectrometer entrance slit is collimated by the first one; the collimated light beam hits a planar diffraction grating and the light dispersed from the grating is focused by the second system, which is concentric with the first. A very simple procedure obtains designs that are anastigmatic for the center of the slit and for a particular wavelength. A specific example shows the performance of this type of spectrometer.

The Offner imaging spectrometer in quadrature.

This is a proposal and description of a new configuration for an Offner imaging spectrometer based on the theory of aberrations of off-plane classical-ruled spherical diffraction gratings. This new spectrometer comprises a concave mirror used in double reflection and a convex reflection grating operating in quadrature, in a concentric layout. A very simple procedure obtains designs that are anastigmatic for a given point on the entrance slit and a given wavelength. Specific examples show that the performance of this type of system improves the performance of analogous conventional in-plane systems, when compactness and/or high spectral resolution is of fundamental importance.