Atomic and electronic structures and stability of icosahedral nanodiamonds and onions

The relative stability of alternative carbon nanoparticles with icosahedral symmetry, such as diamond-like nanocrystallites and multiwalled fullerenes (onions), is investigated using the parametric model and the density functional tight-binding (DFTB) method. It is demonstrated that an increase in the size of particles and their hydrogenation favor the stabilization of diamond-like nanocrystallites. The formation of “intermediate” nanostructures consisting of diamond-like nanocrystallites inside the fullerene cage is revealed. The electronic spectra of icosahedral carbon nanoparticles are calculated.     

Splitting of Spectra in Anharmonic Oscillators Described by Kratzer Potential Function

A perturbation theory model that describes splitting of the spectra in highly symmetrical molecular species in electrostatic field is proposed. An anahrmonie model of a two-dimensional oscillator having Kratzer potential energy function is used to model the molecular species and to represent the unperturbed system. A selection rule for the radial quantum number of the oscillator is derived. The eigenfunctions of a two-dimensional anharmonic oscillator in cylindrical coordinates are used for the matrix elements representing the probability for energy transitions in dipole approximation to be calculated. Several forms of perturbation operators are proposed to model the interaction between the polyatomic molecular species and an electrostatic field. It is found that the degeneracy is removed in the presence of the electric field and spectral splitting occurs. Anharmonic approximation for the unperturbed system is more accurate and reliable representation of a reaJ polyatomic molecular species.     

The IR reflectance spectra of the nu 3(SO4(2-)) and nu 4(SO4(2-)) band regions of some Tutton salts using polarized radiation: testing the model dielectric function

The investigation of the vibrational bands of the SO(4)(2-) ions (in the nu(3) and nu(4) frequency regions) of six different Tutton salts was performed with specular IR reflectance spectroscopy using polarized radiation, on single crystal samples. The reflectance function under oblique incidence using dielectric model function as parameter (originally derived for optically uniaxial crystals) appeared to be readily applicable for the investigated monoclinic crystals. The frequencies of the transversal and longitudinal phonons were obtained by fitting of spectra recorded from (0 1 0), (0 0 1) and (1 0 0) crystal planes. Further, the symmetry types of all experimentally detected phonons were identified. Some of the results were further confirmed from IR absorption spectra recorded at liquid nitrogen temperature (LNT) of isomorphously isolated SO(4)(2-) ions into the corresponding selenate matrices.     

Isosbestic-like point in the polarized reflectance spectra of monoclinic crystals--A quantitative approach

If two overlapping bands originate from transition moments that are perpendicular and lie along the principal axes of the infinity frequency dielectric tensor, an isosbestic-like point (ILP) appears in the overlaid polarized IR reflectance spectra of single crystals. These conditions can also be met in principle in case of the reflectance from the ac-plane of a monoclinic crystal despite of the crystal's low symmetry. In order to determine the transition moment directions, diagonalization of the infinity frequency dielectric tensor should be performed. It is shown that a critical magnitude for the appearance of ILP is the angle of incidence. An increase of this angle leads to a transformation of the ILP to an isosbestic-like region, which eventually vanishes at higher incidence angles. Polarized reflectance spectra of gypsum (CaSO4.2H2O), recorded from the ac crystal face, were used to verify the theoretical results.     

IR specular reflectance spectra of KHSO4 single crystal—Dispersion analysis

Polarized specular reflectance IR spectroscopy was used to provide answers regarding dielectric, vibrational and optical properties of the KHSO₄ single crystal. Applying this technique, spectra with polarization along the principal dielectric axes were recorded. It is shown that reflectance IR spectra at arbitrary direction of polarization recorded from one of the principal planes can be easily calculated if the reflectance spectra along the corresponding two principal axes are known. Using dispersion analysis of the reflectance spectra recorded along the principal dielectric axes and employing downhill simplex iteration method, energy loss function together with the real and imaginary parts of the complex index of refraction and the permittivity tensor were obtained. Employing this data, LO-TO splitting of the modes was further calculated. Discussion concerning the assignment of the bands and its relation to the structure is also given.     

Characterization of partially inverse spinel ZnFe2O4 with high saturation magnetization synthesized via soft mechanochemically assisted route

ZnFe₂O₄ was prepared by a soft mechanochemical route from two starting combinations of powders: (1) Zn(OH)₂/α-Fe₂O₃ and (2) Zn(OH)₂/Fe(OH)₃ mixed in a planetary ball mill. The mechanochemical treatment provoked reaction leading to the formation of the ZnFe₂O₄ spinel phase that was monitored by XRD, TEM, IR and Raman spectroscopy. The spinel phase was first observed after 4 h of milling and its formation was completed after 18 h in both the cases of starting precursors. The synthesized ZnFe₂O₄ has a nanocrystalline structure with a crystallite size of about 20.3 and 17.6 nm, for the cases (1) and (2), respectively. In the far-infrared reflectivity spectra are seen four active modes. Raman spectra suggest an existence of mixed spinel structure in the obtained nanosamples. In order to confirm phase formation and cation arrangement, Mössbauer measurements were done. Estimated degree of inversion is about 0.58 for both starting mixtures. The magnetic properties of the prepared ZnFe₂O₄ powders were also studied. The results show that the samples have a typical superparamagnetic-like behavior at room temperature. Higher values of magnetization in the case of samples obtained with starting mixture (2) suggest somewhat higher degree of cation inversion.