Comparison of the Dynamics of Water Molecules in Crystals of Proton-Ordered Ice IX and Its Proton-Disordered Analog III

A computer simulation of proton-ordered ice IX and its proton-disordered analog III (768 molecules, 90 K) was carried out by the molecular dynamics method using Poltev–Malenkov's potential. For ice IX, the differences in the dynamic characteristics of molecules with O(1) and O(2) are much wider than those in the case of ice III. The libration spectrum of ice IX has a number of distinct acute peaks, and the spectrum of ice III is strongly smoothed. These peculiarities are explained by the proton ordering of ice IX and disordering of ice III. The latter is responsible for the great differences in the short- and especially long-range environment of water molecules in ice crystals and hence for the presence of many molecules with different dynamic characteristics. Thus averaging over a large number of different vibrational spectra of molecules leads to a smoothed total spectrum in the case of the proton-disordered crystal modification of ice.     

The IINS/quantum chemical studies of 17α- and 21-hydroxy-derivatives of progesterone

The inelastic incoherent neutron scattering and quantum chemical studies have been performed on 17 and 21 hydroxy progesterone and the assignment of internal modes have been proposed in the range up to 700 cm⁻¹. The lattice branch of PDS reveals modes which could be attributed to torsions of rings A and D (cyclohexane and cyclopentane) of the pregnane skeleton. An assignment of the torsional vibrations of methyl groups in the range 150–300 cm⁻¹ and the deformation and out-of plane vibrations of CCOH groups has been proposed. An analysis of the effect of hydrogen bonds on PDS spectra has been performed.     

Polymorphism and Conformational Equilibrium of Nitro-Acetophenone in Solid State and under Matrix Conditions

Conformational and polymorphic states in the nitro-derivative of o-hydroxy acetophenone have been studied by experimental and theoretical methods. The potential energy curves for the rotation of the nitro group and isomerization of the hydroxyl group have been calculated by density functional theory (DFT) to estimate the barriers of the conformational changes. Two polymorphic forms of the studied compound were obtained by the slow and fast evaporation of polar and non-polar solutions, respectively. Both of the polymorphs were investigated by Infrared-Red (IR) and Raman spectroscopy, Incoherent Inelastic Neutron Scattering (IINS), X-ray diffraction, nuclear quadrupole resonance spectroscopy (NQR), differential scanning calorimetry (DSC) and density functional theory (DFT) methods. In one of the polymorphs, the existence of a phase transition was shown. The position of the nitro group and its impact on the crystal cell of the studied compound were analyzed. The conformational equilibrium determined by the reorientation of the hydroxyl group was observed under argon matrix isolation. An analysis of vibrational spectra was achieved for the interpretation of conformational equilibrium. The infrared spectra were measured in a wide temperature range to reveal the spectral bands that were the most sensitive to the phase transition and conformational equilibrium. The results showed the interrelations between intramolecular processes and macroscopic phenomena in the studied compound.     

Raman light scattering,infrared absorption and neutron scattering studies of the phase transition and reorientational dynamics of H2O ligands and ClO4↙ anions in [Ca(H2O)4](ClO4)2

Vibrational-reorientational dynamics of H₂O ligands and ClO₄^↙ anions in the high-, intermediate- and low-temperature phases of [Ca(H₂O)₄](ClO₄)₂, detected previously by differential scanning calorimetry (DSC) method, were investigated. The following experimental methods were applied to achieve the goal: middle-infrared (FT-MIR), Raman spectroscopy (RS) and inelastic incoherent neutron scattering (IINS). FT-MIR and RS spectra versus temperature show distinct changes in full-width-at-half-maximum (FWHM) of some bands connected with vibrational modes of ClO₄^↙ and [Ca(H₂O)₄]²⁺ ions. It suggests that in the high temperature phase these ions (and also the ligands from complex cation) perform fast (picoseconds correlation time scale, which is characteristic for optical spectroscopy) stochastic reorientational motions, however in the lower temperatures the speed of these motions is slowed down. Moreover, the splitting of some bands accompanying the observed phase transitions. The comparison of the results obtained by these complementary methods was made. Additionally, IR, RS and IINS spectra were calculated by the DFT method and an excellent agreement with the experimental data was obtained using CASTEP plane-wave periodic boundary condition code. The bands were assigned based on analysis of the phonon eigenvectors obtained from CASTEP calculations.