Analytical Azo Coupling Reactions: A Quantum-Chemical Consideration

Azo coupling reactions of 1-aminonaphthalene with naphthalene-1-diazonium and 4-sulfobenzene-diazonium cations are studied by quantum chemistry. It is found that the reactions are orbital controlled and their regioselectivity is unambiguously governed by the thermodynamic properties of the intermediate σ-complexes and by the effect of the aqueous medium. The latter causes high site selectivity, providing the choice of one of the two possible reaction channels predicted on the basis of quantum-chemical calculations of the isolated molecular systems. As a result, azo coupling occurs at the 4-position of the 1-aminonaphthalene molecule. Additionally, the aqueous medium provides the selection of analytical forms, namely, the protonated azo coupling products that have the quinone-hydrazone structure. On the basis of the quantum-chemical study, the analytical performances of the two azo coupling reactions mentioned above are discussed.     

An Electrostatic Bond Energy Model for Enthalpies of Formation of Chloroalkanes in Gaseous States

An electrostatic bond energy model is formulated to fit the enthalpies of formation and dipole moments of the alkanes and chloroalkanes. In this model, the charge distributions are calculated by an electrostatic approach similar to the "MSE" method, and the enthalpy of formation of a molecule is the sum of the bond energy terms plus the electrostatic energy of the interactions between the charges on all atoms. All parameters of this model are obtained by parameterization. The calculated dipole moments for 13 chloroalkanes and enthalpies of formation for 19 alkanes and non-geminal chloroalkanes agree with the determined values very well. To calculate the enthalpies of formation of geminal chloroalkanes, a correction mainly attributed to the van der Waals interactions in the geminal substituted group, about 24 kJ/mol per pair of geminal chlorine atoms, is introduced.     

Study of the mechanism of recyclization of furans into thiophenes and selenophenes in conditions of acid catalysis. 5. Direction of protonation of furans

2,5-Dimethyl-3-D-furan was prepared for the first time. Its recyclization into the corresponding thiophene and selenophene was investigated. The possibility of -C-protonation of the furan ring was confirmed by experimental and quantum chemical data.See [1] for Communication 4.Scientific-Research Institute of Chemistry, N. G. Chernyshevskii Saratov State University, Saratov 410026. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1030–1034, August, 1997.     

Chemical-potential dependence of the pairing gap in a nuclear-matter slab

The equation for the pairing gap Δ in a slab of nuclear matter governed by the Paris nucleon-nucleon potential is solved for various values of the chemical potential μ in the range from −8 MeV, which corresponds to stable nuclei, to −0.1 MeV, which corresponds to nuclei in the vicinity of the nucleon drip line. The slab is placed in a one-dimensional Woods-Saxon potential whose parameters are set to values typical of nuclei. Two models are considered. In the first, the potential-well depth is fixed at U ₀ = −50 MeV, the density within the slab growing as |μ| is reduced. In the second model, the density is fixed at the center of the slab, |U ₀| decreasing as |μ| is reduced. The behavior of the gap Δ as a function of μ is model-dependent. In the first model, Δ decreases with decreasing |μ|, while, in the second, it increases. At the same time, the effect of the surface enhancement of Δ becomes more pronounced with decreasing |μ| in both models. Original Russian Text ? S.S. Pankratov, E.E. Saperstein, M.V. Zverev, 2006, published in Yadernaya Fizika, 2006, Vol. 69, No. 12, pp. 2052–2063.     

Coupled-channel analysis for 20.4 MeV energy of p-<Superscript>64</Superscript>Zn inelastic scattering

In this study, a coupled-channel (CC) analysis of the elastic and the inelastic scattering of 20.4 MeV polarized protons from a ⁶⁴Zn target leading to the deformed 2⁺, 3−, 2₂⁺2_2^+ states was performed. The CC potential parameters and the deformation parameters of the excited states corresponding to the best fit to the experimental differential cross-sections and the analysing powers data were determined. For 2₂⁺2_2^+ excited state, a mixed type was used and a good fit to the data was provided. The CC calculation results were compared to the pure distorted wave Born approximation (DWBA) calculation results which were calculated using the new parameters. All calculations were conducted using the computer code ECIS06.     

Effect of hydrogenation on spin-reorientation phase transitions and magnetic anisotropy constants of RFe11Ti single crystals (R=Lu, Ho, and Er)

The magnetic anisotropy and spin-reorientation phase transitions in single crystals of the RFe₁₁Ti (R=Lu, Ho, and Er) compounds and their hydrides are investigated. Measurements are carried out on capacitance and torque magnetometers. The magnetic anisotropy constants K ₁ and K ₂ are determined by the mathematical processing of experimental magnetization curves in terms of the phenomenological theory of the anisotropic ferromagnet magnetization. It is demonstrated that the hydrogenation strongly affects the magnitude and the sign of magnetic anisotropy constants, as well as the spin-reorientation phase transitions. The hydrogenation of the HoFe₁₁Ti compound leads to the change in sign of the magnetic anisotropy constant K ₁. The inference is made that a change in the atomic volume and the axial ratio c/a cannot result in the observed effects. A change in the magnetic anisotropy constants upon hydrogenation is primarily due to the change in the interaction of the quadrupole moment of a 4f electron subshell of rare-earth ions with surrounding ions of the crystal lattice and also with valence and conduction electrons.     

The asymptotic behavior of the solutions of variational problems in domain with “accumulators”

Translated from Teoriya Funktsii, Funktsional'nyi Analiz i Ikh Prilozheniya, No. 54, pp. 97–105, 1990.     

Q-switched Yb Doped Fiber Ring Laser with a M-Z Interferometer

An all-fiber Yb-doped Q-switched fiber ring laser system is reported. The laser system uses an all-fiber M-Z interferometer which plays both roles of Qswitch and tunable filter. Theoretical analysis and primary experimental results are given. A continuous tuning range 6fover 7 nm (from 1035 nm to 1042 nm) and a very stable pulse train with repetition rates exceeding 3 kHz and pulse width of 1.1μs were obtained. The laser system shows low cavity loss and is stable.