Accuracy and efficiency of electronic energies from systematic molecular fragmentation

A systematic method for approximating the ab initio electronic energy of molecules from the energies of molecular fragments is tested on a large sample of typical organic molecular structures. The detailed methods, including some additional refinements for molecular rings and long range interactions, are described. The accuracy and computational efficiency of the systematic hierarchy of methods are reported.     

Synthesis and hydroxydeamination in the series of 6-aryl- and 6-benzoimidazolyl-7-aminoazolo[5,1-c]-1,2,4-triazines

The replacement of the amino group with the hydroxy group was examined in the series of 6-aryl- and 6-benzoimidazolyl-7-aminoazolo[5,1-c]-1,2,4-triazines. These reactions provide a convenient synthetic procedure for the preparation of fused azolo[5,1-c]-1,2,4-triazin-7-ones.     

Body shape with minimum total radiant energy flux toward its surface

During a space vehicle's entry into a planet's atmosphere at hypersonic speed one of the important problems is the aerodynamical surface heating due to convective and radiant heat fluxes from the gas after passing through a strong shock wave. Due to the high destructive action of this heating, an important problem is the selection of the aerodynamic shape allowing the minimum heat influx to its surface. The problem of determining the shapes of an axisymmetric body from the condition of minimum total convective heat flux along the lateral face of the body was considered under various assumptions in [1–7]. There are a number of entry conditions (for example, into the earth's atmosphere with a speed of 11 km/ sec at an altitude of about 60 km [12]) during which the radiative component becomes dominant in the total heat flux toward the body. A numerical solution of the problem of hypersonic flow of a nonviscous, non-heat-conducting radiating gas around a body is obtained at this time only for a limited class of bodies and primarily for certain entry conditions (for example, [8–12]). On the basis of these calculations it is impossible to make general conclusions concerning arbitrary body shapes. Therefore, approximate methods were proposed which permit the distribution of radiant heat flux to be obtained for an arbitrary axisymmetric body in a wide range of flight conditions [13–15]. In the present work an expression is derived for the total radiant heat flux over the entire body surface and similarity criteria are found. A variational problem is formulated to determine the shape of an axisymmetric body from the condition of minimum total radiant-heat flux over the entire body surface. It is solved analytically for the class of thin bodies and in the case of a strongly radiating gas.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 4, pp. 84–89, July–August, 1976.     

Polar addition of perfluoro-tert-hexyl iodide to alkenes and alkynes

The effective charges on the atoms in molecules of perfluoroalkyl halides of general formula (CF₃)_nCF_3–nX (X=Cl, Br, I) have been calculated by the AM1 semiempirical method. In polar solvents perfluoro-tert-hexyl iodide is reduced under the action of alkenes and aromatic hydrocarbons to form 2-hydroperfluoro-2-methyl-pentane and perfluoro-2-methyl-2-pentene. In ethyl acetate the regio- and stereo-specific addition of perfluoro-tert-hexyl iodide to alkenes, butadiene, and alkynes takes place, which is associated with the realization of a polar ion-radical mechanism for the reaction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2057–2061, September, 1989.     

Local atomic structure of Cu(In x Ga1−x )Se2 (x = 0.25, 0.5, and 0.75) systems for solar cells

The local atomic structure of thin surface layers of crystalline quasi-binary Cu(In _x Ga_1?x )Se₂ solid solutions was studied by SIMS and EXAFS techniques. The SIMS method showed that the elemental composition of the sample changes most significantly in thin layers at a depth of 5–10 nm; in deeper layers, the component concentrations correspond to the bulk values. The EXAFS method in the x-ray fluorescence mode showed that the results obtained are in agreement with the assumption that quaternary crystalline quasi-binary Cu(In _x Ga_1?x )Se₂ solid solutions exhibit local disorder while average long-range order is detected from x-ray diffraction data.     

A new approach to the synthesis of lamotrigine and other 3,5-diamino-1,2,4-triazine derivatives

A new in principle method for the synthesis of 6-aryl(hetaryl)-3,5-diamino-1,2,4-triazines by decomposition of pre-synthesized tetrazolo[1,5-b][1,2,4]triazines was developed. The advantages of this method over traditional methods were demonstrated using the synthesis of a modern antiepileptic preparation lamotrigine, as an example.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 713–719, March, 2005.     

Determination of the parameters of atomic pair correlations in nickel oxide films by the electron energy loss fine structure method

The electron energy loss extended fine structure (EELFS) spectra were obtained from the pure nickel surface (M _2,3 EELFS) of a stoichiometric NiO film (NiM _2,3 and OK EELFS spectra) and the “nonhomogeneous” oxide film on the surface of nickel Ni-O (NiM _2,3 and OK EELFS spectra). The amplitudes and intensities of electron transitions for the core levels of atoms were calculated with regard for the multiplicity of electron impact excitation of the corresponding core levels of atoms. The corresponding normalized oscillating terms were isolated using the results of calculations based on the experimental EELFS spectra. Agreement between the experimental and calculated (on Ni and NiO test objects) data showed that the theoretical approaches used and the calculated data for describing the EELFS spectra are good approximations. Using the results of calculations and the parameters of secondary electron elastic scattering (FEEF-8 data) we obtained the atomic pair correlation functions from the experimental normalized oscillating parts of the EELFS spectra by Tikhonov’s regularization method.     

Oxidative properties of perfluoroalkyl halides

On the basis of half-wave potential values E_1/2 it was shown that perfluoroalkyl halides have pronounced oxidative properties in comparison with unfluorinated analogs. Tertiary perfluoroalkyl iodides, having a higher oxidation potential than iodine, react with I^– by a scheme including one-electron transfer.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2222–2224, October, 1989.