Roberto Gangemi

NIR‐VCD, vibrational circular dichroism in the near‐infrared: Experiments, theory and calculations

The first well documented experiments of Near Infrared Vibrational Circular Dichroism (NIR-VCD) were performed around 1975. We review the thirty year history of NIR-VCD, encompassing both instrumental development and theoretical/computational methods that allow interpretation of experimental spectra, harvesting useful structural information therefrom. We hope to stimulate interest in this still scarcely explored spectroscopy of chiral molecules.

An operative approach to correct CD spectra distortions due to absorption flattening

We discuss the influence of absorption flattening (AF) on CD spectra, aiming at finding a simple way to compensate the induced distortions. A simple algebraic formalism is proposed based on an unconventional measuring approach, which makes use of a commercial unit. Validation of the proposed compensation method for AF is conducted not only on the already studied CD Vis spectral region of a Co chiral complex with the use of an AF emulator, but also on the far UV CD spectra of poly-L-glutamic acid suspensions with different turbidity levels. Comparison with some correction factors proposed in the literature is presented.

Dipole and rotational strengths for overtone transitions of a C2-symmetry HCCH molecular fragment using Van Vleck perturbation theory

Contact transformation theory up to second order is employed to treat CH-stretching overtone transitions and to calculate dipole and rotational strengths. A general Hamiltonian describing two interacting CH-stretching oscillators is considered, and the Darling–Dennison resonance is appropriately taken into account. The two CH bonds are supposed to be dissymmetrically disposed, so as to represent a chiral HCCH fragment, endowed with C2 symmetry. Analytical expressions of transition moments and dipole and rotational strengths are given in the hypothesis of general electric and magnetic dipole moments with quadratic dependence on coordinates and momenta. Dipole and rotational strengths are then calculated together with frequencies for the fundamental and first three overtone regions in the simplifying hypothesis of the valence optical approach on the coupled-oscillator framework. Simplified analytical expressions thereof in the relevant parameters are presented.

Electronic and vibrational circular dichroism spectra of chiral 4-X-[2.2]paracyclophanes with X containing fluorine atoms.

The absorption IR and vibrational circular dichroism (VCD) spectra of both enantiomers of 4-X-[2.2]paracyclophanes (X = F, CH(2)F, COCF(3)) have been recorded in the mid-IR and CH stretching regions. The electronic CD (ECD) spectra have been collected as well. VCD spectra in the two IR regions, 900-1700 cm(-1) and 2700-3200 cm(-1), have been compared with the corresponding DFT calculated spectra. The absolute configuration assignment was confirmed as previously determined. We have shown that, to various extents, the VCD and ECD spectra bear some information on the relative mobility of the two phenyl rings and on the existence of different conformers for the X group. It has been observed that X = F and X = CH(2)F groups do not change the conformational and electronic properties of the parent X = H and X = CH(3) molecules. The X = COCF(3) group brings in a large perturbation to the [2.2]paracyclophanes, and the role of fluorine is less important than that of oxygen.

Agreement of classical Kubo theory with the infrared dispersion curves n(ω) of ionic crystals

The theoretical dispersion curves (refractive index vs. frequency) of ionic crystals in the infrared domain are expressed, within the Green-Kubo theory, in terms of a time correlation function involving the motion of the ions only. The aim of this paper is to investigate how well the experimental data are reproduced by a classical approximation of the theory, in which the time correlation functions are expressed in terms of the ions orbits. We report the results of molecular-dynamics (MD) simulations for the ions motions of a LiF lattice of 4096 ions at room temperature. The theoretical curves thus obtained are in surprisingly good agreement with the experimental data, essentially over the whole infrared domain. This shows that at room temperature the motion of the ions develops essentially in a classical regime.

Electrical and mechanical anharmonicities from NIR-VCD spectra of compounds exhibiting axial and planar chirality: The cases of (S)-2,3-pentadiene and methyl-d3 (R)- and (S)-[2.2]paracyclophane-4-carboxylate†

The IR and Near infrared (NIR) vibrational circular dichroism (VCD) spectra of molecules endowed with noncentral chirality have been investigated. Data for fundamental, first, and second overtone regions of (S)-2,3-pentadiene, exhibiting axial chirality, and methyl-d(3) (R)- and (S)-[2.2]paracyclophane-4-carboxylate, exhibiting planar chirality have been measured and analyzed. The analysis of NIR and IR VCD spectra was based on the local-mode model and the use of density functional theory (DFT), providing mechanical and electrical anharmonic terms for all CH-bonds. The comparison of experimental and calculated spectra is satisfactory and allows one to monitor fine details in the asymmetric charge distribution in the molecules: these details consist in the harmonic frequencies, in the principal anharmonicity constants, in both the atomic polar and axial tensors and in their first and second derivatives with respect to the CH-stretching coordinates.

Infrared optical properties of α quartz by molecular dynamics simulations

This paper is concerned with theoretical estimates of the refractive-index curves for quartz, obtained by the Kubo formulae in the classical approximation, through MD simulations for the motions of the ions. Two objectives are considered. The first one is to understand the role of nonlinearities in situations where they are very large, as at the structural phase transition. We show that, on the one hand, they do not play an essential role in connection with the form of the spectra in the infrared. On the other hand, they play an essential role in introducing a chaoticity which involves a definite normal mode. This might explain why that mode is Raman active in the α phase, but not in the β phase. The second objective concerns whether it is possible in a microscopic model to obtain normal mode frequencies, or peak frequencies in the optical spectra, that are in good agreement with the experimental data for quartz. Notwithstanding a lot of effort, we were unable to find results agreeing better than about 6%, as apparently also occurs in the whole available literature. We interpret this fact as indicating that some essential qualitative feature is lacking in all models which consider, as the present one, only short-range repulsive potentials and unretarded long-range electric forces.

Persistence of regular motions for nearly integrable Hamiltonian systems in the thermodynamic limit

A review is given of the studies aimed at extending to the thermodynamic limit stability results of Nekhoroshev type for nearly integrable Hamiltonian systems. The physical relevance of such an extension, i. e., of proving the persistence of regular (or ordered) motions in that limit, is also discussed. This is made in connection both with the old Fermi–Pasta–Ulam problem, which gave origin to such discussions, and with the optical spectral lines, the existence of which was recently proven to be possible in classical models, just in virtue of such a persistence.