Fluorescence Characteristics of Schiff Bases Derived from Amino- and Aminoalkylpyridines

The fluorescence characteristics of the Schiff bases 2-(3-pyridylmethyliminornethyl)phenol (1), 2-(2 pyridyliminomethyl)phenol (2), N.N-bis(salicylidene)-2,3-pyridinediamine (3), N,N'-bis(salicylidene)-2,6-pyridinediamine (4) and 2-(2-amino-4-methoxymethyl-6-methyl-3-pyridylmethyliminomethyl)phenol (5) were studied in various solvents at different pH values. Corresponding quantum efficiencies were determined. Compound 1, which showed a tendency towards tautomeric mterconversion to ketoamine in polar protic solvents, was not fluorescent at pH < 8. The fluorescence of other compounds was very sensitive to solvent polarity and the pH of the medium. Compounds 2-4, preferably present as enolimines in all solvents, were not fluorescent in non-polar and moderately polar solvents, whereas weak emission was observed in polar solvents, like methanol, dimethylformamide and dioxane/water 1/1 (0.001 < Q < 0.072). A significant increase in Stokes shifts and in quantum efficiencies was noted as a result of increasing polarity of dioxane/water mixtures, indicating specific interactions with polar water molecules. The emission was promoted at acidic pH values where a pyridinium cation was formed (0.061 < Q < 0.519, in dioxane/water 1/1 at pH 3.4). Compound 5, which was a tautomeric mixture of enoiimine and cyclic diamine in all solvents, was fluorescent in polar as well as in non-polar media. The quantum efficiency varied dependent on the solvent and pH (0.023 <Q< 0.435). The cyclic diamine, i. e. the more rigid structure was supposed to be responsible for the fluorescence in non-polar and aprotic solvents as well as at neutral, and weakly basic pH values.     

Anomalous lateral beam shift and total absorption due to excitation of surface waves in materials with negative refraction

We studied electromagnetic beam reflection from layered structures that include materials with negative refraction. Excitation of leaky surface waves leads to the formation of anomalous lateral shifts in the reflected beams with single or double peak structures. The presence of reasonable losses within material with negative refraction, besides significant influence on manifestation of the giant lateral shifts, can lead to their total suppression and anomalously high absorption of the incident radiation. If, in addition to the resonant excitation of leaky surface waves, radiation inflow exactly compensates their irreversible damping, total absorption of the incoming radiation can be achieved for moderately wide beams.     

Interaction of counterpropagating discrete solitons in a nonlinear one-dimensional waveguide array

We experimentally investigate the interaction of counterpropagating discrete solitons in a one-dimensional waveguide array in photorefractive lithium niobate. While for low input powers only weak interaction and formation of counterpropagating vector solitons are observed, for higher input powers a growing instability results in discrete lateral shifting of the formed discrete solitons. Numerical modeling shows the existence of three different regimes: stable propagation of vector solitons at low power, instability for intermediate power levels leading to discrete shifting of the two discrete solitons, and an irregular temporal dynamic behavior of the two beams for high input power.     

Maximum entropy principle for rarefied polyatomic gases

The aim of this paper is to show that the procedure of maximum entropy principle for the closure of the moments equations for rarefied monatomic gases can be extended also to polyatomic gases. The main difference with respect to the usual procedure is the existence of two hierarchies of macroscopic equations for moments of suitable distribution function, in which the internal energy of a molecule is taken into account. The field equations for 14 moments of the distribution function, which include dynamic pressure, are derived. The entropy and the entropy flux are shown to be a generalization of the ones for classical Grad’s distribution. The results are in perfect agreement with the recent macroscopic approach of extended thermodynamics for real gases.     

Thermal collapse of spin polarization in half-metallic ferromagnets

We propose two novel approaches to study the temperature dependence of the magnetization and the spin polarization at the Fermi level in magnetic compounds, and apply them to half-metallic ferromagnets. We reveal a new mechanism, where the hybridization of states forming the half-metallic gap depends on thermal spin fluctuations and the polarization can drop abruptly at temperatures much lower than the Curie point. We verify this for NiMnSb by ab initio calculations. The thermal properties are studied by mapping ab initio results to an extended Heisenberg model which includes longitudinal fluctuations and is solved by a Monte Carlo method.     

Theoretical analysis of the experimental UV-Vis absorption spectra of some phenolic Schiff bases

The time-dependent density functional theory (TDDFT) was applied in conjunction with the natural bond orbital analysis to examine the UV-Vis properties of 10 phenolic Schiff bases. The calculations were performed with different functionals, but main discussion refers to results obtained at the B3LYP/6-311+G(d,p) level of theory. The approach based on the natural localised molecular orbital clusters indicates similar behaviour for majority of examined compounds. The HOMO (“highest occupied molecular orbital”) cluster is delocalised over the ring which is electron richer, the HOMO-1 cluster is spread over the other ring, whereas the LUMO (“lowest unoccupied molecular orbital”) cluster is situated on the imino group. The two bands at long wavelengths correspond to the HOMO → LUMO and HOMO-1 → LUMO transitions, i.e. from both A and B rings to the imino group. The next band originates from a transition from the imino group to the imino group. The band at the smallest wavelengths originates from a transition from the A ring to the A ring, or from the B ring to the B ring. Our findings are in very good agreement with the existing literature data.