Quantum-chemical study of the electronic structure of adamantane and the 1-adamantyl cation,anion, and radical

The spatial and electronic structures of the adamantane molecule (AdH), the 1-adamantyl radical (1-Ad^.), the 1-adamantyl cation (1-AD⁺), and the 1-adamantyl anion (1-Ad^–) have been calculated by the SCF-MO-LCAO method in the all-valence-electron MINDO approximation. The calculated heats of formation attest to the fact that the homolytic cleavage of the C-H bond is energetically most advantageous in the gaseous phase or in nonpolar inert solvents. The formation of a 1-Ad^–, H⁺ pair is associated with the largest expenditure of energy due to the large ionization potential of the hydrogen atom.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 3, pp. 357–360, May–June, 1989.     

The influence of the cation on the structure of the triiodosilver(I) anion

Complexes of the type M₂AgI₃ (M = K, NH₄, me₄N, et₄ N, pr₄ N and bu₄ N) have been prepared and characterized. The Raman spectrum of the AgI₃²⁻ anion has been interpreted in terms of a C_3ν symmetry. Splittings of the E modes are observed in the solid state, presumably due to a lowering of the symmetry. The influence of the size of the cation is studied.     

The electronic structure and properties of pyrazine,its cation,and anion

Gaussian orbital LCAO MO calculations are reported for pyrazine in its ground and first excited triplet state, together with calculations on its anion and cation. Energies, population analysis indices, and one-electron properties are compared across the series in order to investigate the differences in electron distribution.     

X-ray spectral and photoelectron study of the electronic structure of copper phthalocyanine and its fluoro-substituted analog

A complex experimental study of Cu(2p _3/2), Cu(2p _1/2) photoelectron and Kα_1,2 and Lα_1,2 X-ray emission spectra of copper in copper phthalocyanine CuPcH₁₆ and its fluoro-substituted analog CuPcF₁₆ is carried out. A charge transfer model is used to interpret the spectra. It is shown that Kα₁ and Kα₂ lines of the spindoublet of copper have a complex structure due to the processes of metal-to-ligand charge transfer. The role of a satellite in the formation of emission lines is revealed.     

Capillary isotachophoretic study of outer-sphere complex formation

Summary Outer-sphere complex formation was studied by capillary isotachophoresis. Strong ion-pair formation between cationic Co(III) complexes such tris(ethylenediamine) Co(III) and dicarboxylic acids was observed. The effect of the cationic Co(III) complex concentration, dissolved in the leading electrolyte, on the sample mobility was shown.Dedicated to Prof. Dr. A Liberti on the occasion of his 70th birthday.     

An X-ray spectral and theoretical study of the electronic structure and features of interatomic interactions in phenoxysilanes

The electronic structure and features of interatomic interactions providing the Si–O–C₆H₅ bonds in H_4-nSi(OC₆H₅)_n (n = 1–4) were studied by a combined analysis of the X-ray emission and photoelectron spectroscopic data and the results of quantum-chemical calculations. Theoretical calculations were carried out using the density functional theory. The distributions of the density of states were constructed, the correlation energy diagrams were presented, and the main types of interatomic interactions in phenoxysilanes were revealed.     

The electronic structure of the disilavinylidene anion

The electronic structure of the disilavinylidene (H₂Si = Si)⁻ anion is investigated with the MC SCF CI and CEPA methods. In addition to the doublet ground state (²B₂) with an electron affinity of 1.65 eV, an excited state (⁴A'') is found which is still stable by about 0.6 eV.     

X-ray photoelectron study of the electronic structure of Fe systems

The possibility of magnetic property investigations and obtaining additional information is examined for compounds with various types of chemical bond, namely, FeX₂ (X = F, Cl, Br), Fe-Ge, Fe₅₀Co₅₀, and Fe₅₀Mn₅₀, using X-ray photoelectron spectroscopy. Translated fromZhurnal Struktumoi Khimii, Vol. 39, No. 6, pp. 1093–1097, November–December, 1998.     

X-ray spectral study of the nature of electronic interactions in transition metal dithiocarbamates

SK_β spectra are studied for a series of nickel(II), zinc(II), and cadmium(II) dithiocarbamate complexes. Model quantum chemical calculations of the electronic structure of planar chelate rings are reported. It is shown that the metal-ligand interaction forming a coordination bond between the dithiocarbamate ligand and the metal mainly involves the nonbonding n-electrons and the weakly bonding π-electrons localized on the sulfur atoms. Translated fromZhurnal Struktumoi Khimii, Vol. 39, No. 6, pp. 1121–1126, November–December, 1998.