Quantum chemistry of many-electron systems: high-priority aspects

The review generalizes the studies devoted to the development of a new quantum chemistry method representing an alternative to the Hartree–Fock approximation. Based on the hypothesis of prohibition of equipotential surfaces, which clarifies the physical sense of the Pauli exclusion principle, and taking account of the condition for antisymmetrical wave function of the triplet state (3S) of He atom, the Hartree–Fock approximation is inappropriate for a priori determination of the nodal surfaces of many-electron wave functions (MWFs) for the test systems traditionally used in quantum chemistry, namely, excited triplet state of H₂ molecule and the ground electronic states of Li atom and LiH molecule. The nodal surfaces of the wave functions corresponding to the minimum basis set of Slater orbitals in the Hartree–Fock approximation are constructed and analyzed. An alternative to the Hartree–Fock approximation is provided by the MWF quantum chemical method being developed by the authors. In the MWF method, the nodal surfaces for H₂(³Σ _u ^v ) and Li(²S) are specified a priori. Some aspects of geometric interpretation of the Pauli exclusion principle are discussed. Unlike the MWF method, the Hartree–Fock approximation is unsuitable for taking account of the dependence of the MWF nodal surfaces on the nuclear charges and on correlation effects related to the motion of electrons with antiparallel spins because such nodal surfaces are predefined by the mathematical properties of Slater determinants rather than by physically clear and more practically valuable algebraic products of electrostatic potential differences.     

Calculation of possible stabilization of glycosyl carbocations in furanosides by different theoretical methods

The paper deals with the comparison of different theoretical methods for the calculation of stabilization energies of glycosyl cations from fucofuranoside glycosyl donors containing different protecting groups at atom O(3). The experimental and calculated data on stereoselectivity of glycosylation were compared. The formation of the stabilized glycosyl cations is considered as one of the possible steps of glycosylation reaction, which exerts influence on the stereoselectivity of the process and makes it possible to obtain difficultly accessible 1,2-cis-glycosides. Semi-empirical and ab initio methods without allowance for the electron correlation underestimate the stabilization energy values. The allowance for the electron correlation in the MP2 approximation, as well as the calculations by density functional theory, allowed us to obtain the data corresponding to the experimentally observed stereoselectivity.     

Quantum chemical studies of azoles 4. A novel elimination–addition mechanism of tetrazole and 1,2,4-triazole electrophilic substitution

Thermodynamic parameters of the addition–elimination and elimination–addition electrophilic substitution reactions of 1H-tetrazole and 1,2,4-1H-triazole obtained from DFT B3LYP/ 6-31G(d,p) quantum chemical calculations with proton as model electrophile are compared. According to calculations, the elimination–addition reactions can proceed without preliminary formation of N-protonated azolium salts.     

Alkylation of toluene with dichloromethane in the presence of triisobutylaluminum and perfluorophenylborates

¹H NMR method showed that in systems based on triisobutylaluminum (TIBA) and triphenylcyclopropenylium [Ph₃C₃]⁺[B(C₆F₅)₄]–(CPB) or triphenylmethylium [Ph₃C]⁺[B(C₆F₅)₄]–(TB) perfluorophenylborates in a toluene–dichloromethane mixture the Friedel–Crafts process occurs with the formation of ditolylmethane (DTM) accompanied by the complete decomposition of TIBA to form isobutane. ¹⁹F NMR spectroscopy showed that the [B(C₆F₅)₄]–anion decomposes in the systems to form B(C₆F₅)₃ and HC₆F₅. The short-living [AlBu₂ ⁱ]+ cation formed in the reaction of perfluorophenylborates with TIBA is assumed to be the species initiating the process. It has been shown that CPB is less reactive than TB. The addition of a stoichiometric amount of Ph₂CCpFluHfMe₂ exerts no effect on the process with the CPB-containing system but inhibits the reaction in the case of TB.     

Chalcogenation of 1,4-dichlorobut-2-yne with organic dichalcogenides in the system hydrazine hydrate–KOH

A reaction of organic dichalcogenides R₂Y₂ (R = Ph, Bn, Pr; Y = S, Se) with 1,4-dichlorobut-2-yne in the system hydrazine hydrate–KOH leads to four principal products: 1,4-bis(organylchalcogenyl)but-2-ynes, 1-organylchalcogenylbut-1-en-3-ynes, 4-organylchalcogenylbut-1-en-3-ynes, and 3(5)-methylpyrazole. The selectivity of the formation of individual products is determined by the ratio of the substrates used and the reaction temperature. A plausible mechanism of chalcogenation considered in the work agrees with the effect of the nature of chalcogene atoms and organic substituents R on stability of intermediates and products. The stabilization of carbanions by α chalcogene-containing groups corresponds to the following order: PhS > PhSe > BnS > BnSe > PrS.     

Interaction of amorphous and crystalline nickel nanoparticles with hydrogen

Nickel nanoparticles were deposited on the surface of highly oriented pyrolytical graphite by laser electrodispersion and precipitation from a solution of reverse micelles. The particles were studied using scanning tunneling microscopy and spectroscopy as well as Auger spectroscopy. The elemental composition of the nanoparticles and specific features of the electronic structure of their surface were determined. Adsorption of molecular hydrogen was also studied.     

Application of polymethyl methacrylate in cathode materials of lithium-ion batteries

A study of the Li₂FeSiO₄/C cathode material doped with Mn demonstrated that introduction of polymethyl methacrylate results in a substantial decrease in the particle size and increase in the specific surface area of the cathode material. Polymethyl methacrylate strongly improves the cyclic stability of the cathode material. The discharge capacity after the first cycle was 218 mA h g^–1, and that upon stabilization of the structure of the cathode material, 170 mA h g^–1.