Effect of squeezed vibrational states on the optical properties of molecular systems in a field of laser radiation

Specific features of optical and nonradiative transitions in molecular systems in the field of an intense electromagnetic wave are studied with account of squeezed vibrational states. It is shown that a field of laser radiation considerably enhances the tunneling processes in electronic vibrational systems and makes it possible to obtain the generation of higher harmonics. Conditions are found under which squeezed vibrational states can lead to some stabilization of excited electronic states with respect to the processes of luminescence.     

Mechanochemical Effects in Processes of Corrosion of Metals

Mechanochemical effects have been investigated in the processes of corrosion of bent plates of unalloyed and high-alloy steel in aqueous solutions of sulfuric and hydrochloric acids. Special attention was paid to the strain sign effect discovered recently and caused by the existence of a surface stress in solids. The use of the weight method and the hydrogen method of corrosion control has yield well consistent results confirming the existence of the mechanochemical effect of the strain sign even under condition of the starting corrosion cracking. The domination of corrosion on the concave side gives evidence of the negative sign of surface stress at the steel/solution boundary, which can be explained by the formation of the electrical double layer.     

Thermodynamic and kinetic theory of ionic micellar systems: 1. Work of aggregation

The previously developed approach to the thermodynamics of molecular aggregates based on the methods of the nucleation theory is extended to including ionic aggregative systems with the choice of the real concentration of monomeric ions of surfactants as a standard concentration of aggregates. Results are also generalized to multicomponent systems and a new expression for the work of aggregation is derived. Three models of ionic aggregates are analyzed, i.e., bare aggregate (containing no counterions), fully dressed aggregate (with maximal number of counterions), and dressed aggregate with arbitrary numbers of counterions. In the consideration of the ionic aggregate as a complex ion that yields simpler ions upon dissociation, the notion of the average activity coefficient of the ionic aggregate is introduced. Characteristics of real dressed ionic aggregates are studied. Restrictions in the use of the model of the dressed ionic aggregate are revealed.     

Mechanochemical effects in redox reactions with participation of iron

The processes of deposition of copper, silver, and lead from their aqueous solutions separately on the concave (contracted) and convex (stretched) sides of a bent steel plate have been investigated. The difference in the deposition rate on the opposite sides gives evidence of the existence of the mechanochemical strain sign effect in redox reactions with the participation of iron.     

Synthesis of 2-aryl-2-trifluoromethyl-1,3-thiazolidin-4-ones and 2-aryl-2-trifluoromethyltetrahydro-4<Emphasis Type="Italic">H</Emphasis>-1,3-thiazin-4-ones and their oxidation with hydrogen peroxide

Reactions of aryl trifluoromethyl ketone imines with 2-sulfanylacetic and 3-sulfanylpropanoic acids afforded 2-aryl-2-trifluoromethyl-1,3-thiazolidin-4-ones and 2-aryl-2-trifluoromethyltetrahydro-4H-1,3-thiazin-4-ones, respectively. Their subsequent oxidation with hydrogen peroxide gave the corresponding 2-aryl-2-trifluoromethyl-1,3-thiazolidin-4-one 1-oxides and 2-aryl-2-trifluoromethyltetrahydro-4H-1,3-thiazin-4-one 1-oxides and 1,1-dioxides.     

Micellization theory based on the law of mass action with a variable aggregation number

Variations in the aggregation number of spherical micelles are considered within the micellization theory based on the law of mass action. The mechanism of micellization in a polydisperse aggregated system and the transition to a monodisperse model are explained. A relation between aggregation numbers and chemical potentials of molecules or ions is determined using the curve for equilibrium distribution of aggregates over the aggregation numbers. It is shown that the aggregation numbers of nonionic surfactants unambiguously grow with concentration; however, such a conclusion cannot be drawn for ionic surfactants. For the explicit concentration dependence of the aggregation number, two versions of an analog of the Langmuir equation are proposed to be used, i.e., versions comprising the total surfactant concentration and the concentration of monomers. Comparison with experimental data is carried out by the example of conventional surfactants, namely, sodium dodecyl sulfate and hexadecyltrimethylammonium bromide.     

Asymptotics of pressure tensor in wedge-shaped film between solids characterized by dispersion forces

Asymptotic equations are derived for all four (three diagonal and one off-diagonal) components of the Irving-Kirkwood pressure tensor in a wedge-shaped film of a fluid located between solid phases characterized by dispersion forces. The equations describe the dependence of the aforementioned components on the position inside the film at large distances from the solid surfaces. It is shown that, when the walls of a slit are of different natures, the pressure tensor depends not only on the opening angle of the wedge-shaped slit, bus also on the position of the interface between the solids in contact outside of the slit. As a consequence, the symmetry of the spatial dependence of the tensor components with respect to the median plane is violated.