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Journal of Structural Chemistry

2015 year, number 3

1.
QUANTUM CHEMICAL CALCULATION OF THE STRUCTURE, DIPOLE MOMENT, AND POLARIZABILITY OF O-METHYL METHYLPHOSPHONOFLUORIDATE IN THE GAS PHASE

A. V. Lebedev
Closed Joint-Stock Company SPETSPRIBOR, Tula, Russia
Keywords: O-methyl methylphosphonofluoridate, quantum chemical calculation, geometric parameters, conformer, dipole moment, polarizability

Abstract >>
Two conformers of O-methyl methylphosphonofluoridate (MMPF) are found. Their geometric parameters, dipole moments, and polarizabilities are calculated. It is shown that the methods and basis sets chosen for phosphoryl compounds not having conformational diversity are applicable to the calculation of the structure and mentioned properties of MMPF conformers. The features of the MMPF structure and stereochemistry are considered.

DOI: http://dx.doi.org/10.1134/S0022476615030014



2.
ELECTRONIC STRUCTURE, CHARGE TRANSFER CHARACTER AND SPECTROSCOPIC PROPERTY OF ELECTROLUMINESCENT/PHOTOLUMINESCENT [ZnL2] (HL = 2-(1 H-BENZO[d]IMIDAZOL-2-YL)-4-BROMOPHENOL) STUDIED BY DENSITY FUNCTIONAL THEORY

Y.-P. Tong, Z. Jin, Y.-W. Lin
Huizhou University, Huizhou, P. R. China
Keywords: Zn(II) chelate complex, 2-(1H-benzo[d]imidazol-2-yl)-4-bromophenol, theoretical calculation, electronic structure, LLCT, TDDFT, DOS/PDOS

Abstract >>
In this paper the DFT-/TDDFT-based theoretical calculation results of the electroluminescence/photoluminescence zinc(II) chelate complex [ZnL2] are presented, including the molecular geometry, electronic structure, charge transfer character of absorption and emission, effect of the Br group on the absorption/emission property and colors. The charge transfer character of Uv-vis absorptions, and the nature of electroluminescence/photoluminescence are all due to the π - π* ligand-to-ligand charge transfer transition (LLCT). The significant effect of the substituted Br group on the absorption/emission property and colors, and the Zn ligand bonding property of the main ionic interaction are analyzed and discussed in detail based on PDOS/OPDOS and the Mulliken population analyses. It is concluded that the introduction of substituted groups should significantly affects the electroluminescence/photoluminescence metal chelate complexes, with their absorption/emission property and colors being tuned.

DOI: http://dx.doi.org/10.1134/S0022476615030026



3.
SUBSTITUENT EFFECTS ON THE ABSORPTION AND VIBRATIONAL SPECTRA OF SOME 2-HYDROXY SCHIFF BASES: DFT/TDDFT, NATURAL BOND ORBITAL AND EXPERIMENTAL STUDY

S.A. Elroby1,2, S. Aboud1, S.G. Aziz1, R. Hilal1,3
1King abdullaziz University, Jeddah, Saudi Arabia
2Benisuef University, Benisuef, Egypt
3Cairo University, Giza, Egypt
Keywords: electronic spectra, vibrational spectra, DFT/TDDFT, solvent and substituent effects, NBO analysis, 2-hydroxy Schiff bases

Abstract >>
The electronic structure of salicylideneaniline (SA) and some of its derivatives are investigated both experimentally and theoretically. The equilibrium geometric structures of the studied compounds are determined at the B3LYP/6-311++G** level of theory. A set of 12 substituted SA derivatives is considered in the present work. The choice of these substituents aims to create a push-pull system on the SA basic structure which would shade light onto its photo physics. The electronic absorption spectra of SA are recorded in the UV-VIS region, in both polar and nonpolar solvents. Assignments of the observed electronic transitions are facilitated via time-dependent density functional theory (TDDFT) computations at the same level of theory. Electronic configurations contributing to each excited state are identified and the relevant MOs are characterized. The extent of delocalization and intramolecular charge transfer are estimated and discussed in terms of natural bond orbitals (NBO) analysis and second order perturbation interactions between donor and acceptor MOs. Solvent effects on the electronic absorption spectra are discussed in terms of the difference in polarizabilities of the ground and excited states. FTIR spectra of SA and its derivatives are measured in KBr platelets. Detailed vibrational assignments are given based on the calculated potential energy distributions. "IR marker bands" that characterize the SA framework are identified. The effect of substituents, the nature of the characteristic "marker bands", and intensity quenching of some bands are discussed.

DOI: http://dx.doi.org/10.1134/S0022476615030038



4.
RAMAN SPECTRA AND STRUCTURE OF (1x)RbNO3 + xAl2O3 SYSTEMS

M. M. Gafurov1, K. Sh. Rabadanov1, M. B. Ataev1, A. R. Aliev2, A. M. Amirov1, Z. Yu. Kubataev1
1Joint Analytical Center, Dagestan Scientific Center, Russian Academy of Sciences, Makhachkala, Russia
2Amirkhanov Institut of Physics, Dagestan Scientific Center, Russian Academy of Sciences, Makhachkala, Russia
Keywords: rubidium nitrate, alumina, Raman spectra, autocorrelation function

Abstract >>
By Raman spectroscopy the structural dynamic properties of rubidium nitrate RbNO3 and its heterogeneous composites with nanosized powder of alumina Al2O3 are studied at different temperatures, phase states, and concentrations of Al2O3 nanopowder. At high concentrations (x ≥ 0.5) of the Al2O3 filler an additional component with a maximum at ν1 ~ 1049 cm1 is detected in the Raman spectrum of the heterogeneous system. It can be assigned to NO3 vibrations located in the near-surface region of Al2O3 nanoparticles. Furthermore, at high concentrations (x ≥ 0.5) of the Al2O3 filler spectral manifestations of phase transitions of crystalline rubidium nitrate RbNO3 disappear. This indicates a radical change in the microstructure of the heterogeneous system in comparison with the homogeneous one.

DOI: http://dx.doi.org/10.1134/S002247661503004X



5.
STRUCTURAL MODIFICATIONS OF VO2+ CHELATES IN THE ORGANIC MATTER OF OILS AND BITUMENS FROM THE EPR SPECTRA

L. G. Gilinskaya1, L. S. Borisova2, E. A. Kostyreva2
1Sobolev Institute of Geology and Mineralogy, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Trofimuk Institute of Petroleum-Gas Geology and Geophysics, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: vanadyl ion complexes, EPR spectra, simulation of superimposed spectra

Abstract >>
Vanadyl metal-organic complexes (VO2+) in genetically different fractions of natural oils and bitumens are studied using EPR. Phenolic vanadyl complexes are identified having an isotropic spectrum with the parameters Ao = 8.82 mT, go = 1.996, as opposed to the previously studied axially symmetric spectra of vanadyl porphyrin complexes with Ao = 9.46 mT, go = 1.976 ( A|| = 16.79 mT, A = 5.78 mT, g|| = 1.964, g = 1.983). The simultaneous presence of both types of vanadyl complexes in the samples under consideration results in a complex spectrum, which is identified by computer simulation using the ESR1 software.

DOI: http://dx.doi.org/10.1134/S0022476615030051



6.
PHOTOELECTRON SPECTRA AND ELECTRONIC STRUCTURE OF BORON DIPROPYL IMIDOYLAMIDINATES

S. A. Tikhonov, V. I. Vovna
Fareastern Federal University, Vladivostok, Russia
Keywords: electronic structure, photoelectron spectroscopy, density functional theory, Koopmans theorem, nitrogen-containing boron complexes, imidoylamidinates, β–diketonates

Abstract >>
The electronic structure of seven boron dipropyl imidoylamidinates is studied by ultraviolet photoelectron spectroscopy and density functional theory. The effect of different substituents at carbon and nitrogen atoms of the chelate ring on the nature and sequence of electronic levels is determined. Unlike their β-diketonate analogues, for nitrogen-containing compounds the absence of a noticeable mixing of orbitals of the benzene and chelate rings is revealed. It is shown that in the energy range up to 10 eV the calculated results corrected for the Koopmans defect reproduce well the energy ranges between the ionized states of the complexes.

DOI: http://dx.doi.org/10.1134/S0022476615030063



7.
COMPUTER SIMULATION OF THE POINT DEFECT FORMATION IN MgSiO3 BASED CERAMIC MATERIALS

A. N. Chibisov
Computing Center, Far Eastern Branch, Russian Academy of Sciences, Khabarovsk, Russia
Keywords: ab initio calculations, defect formation, structural characteristics

Abstract >>
The Schottky point defect formation in MgSiO<sub>3</sub>-based ceramics is studied by the density functional theory method. It is shown that the formation of a Mg vacancy at the Mg2 position is more energy-efficient than at the Mg1 position by nearly 1 eV. The silicon vacancy has the highest energy of formation. The most energy-efficient defect is the oxygen vacancy at the O3 position in the enstatite lattice. The results of the effect of atom vacancies on the structural characteristics of MgSiO<sub>3</sub> are shown.

DOI: http://dx.doi.org/10.1134/S0022476615030075



8.
CRYSTAL STRUCTURE AND ANTITUMOR ACTIVITIES OF THE DICHLORIDE 2,6-bis(1-PHENYLBENZIMIDAZOL-2-YL)PYRIDINE COPPER(II) COMPLEX

Q.-W. Huang1, S.-G. Liu1, G.-B. Li1, S.-X. Wang2, W.-Y. Su1, D.-M. Liang1, S.-Q. Mao1
1Lingnan Normal University, Zhanjiang, P.R. China
2Shenzhen University, Shenzhen, P.R. China
Keywords: benzimidazole, copper complex, crystal structure, antitumor activities

Abstract >>
A new complex Cu(bpbp)Cl2×DMF×H2O is synthesized by treatment of CuCl2 with 2,6-bis(1-phenylbenzimidazol-2-yl)pyidine in DMF. Its structure is characterized by elemental, IR, UV, and single crystal X-ray structure analyses. For the complex: crystal system, triclinic, space group P ī, a = 1.0537(1) nm, b = 1.1735(1) nm, c = 1.3749(2) nm, α = 112.275(2), β = 91.531(2), γ = 97.700(2), V = 1.553(4) nm3, Z = 2. In a distorted trigonal bipyramidal geometry the Cu(II) ion is coordinated by three nitrogen atoms from 2,6-bis(1-phenylbenzimidazol-2-yl)pyridine and two chloride ions. The antiproliferative activities of the complex are screened by MTT assay against HepG2, Huh7, Eca109, and Eca9706 cancer cells. The complex exhibits specific inhibition on Eca9706 cancer cells with the IC50 value of 28 mM after 48 h treatment. CCDC: 968927.

DOI: http://dx.doi.org/10.1134/S0022476615030087



9.
STRUCTURAL CHARACTERIZATION OF TETRAKIS(1,3-DIAZINANE-2-THIONE)CADMIUM(II) SULFATE

R. Mahmood1, S.G. Hussain2, A.A. Isab3, M. Fettouhi3, A. Fazal3, S. Ahmad2
1University of Azad Jammu and Kashmir, Chela Campus, Muzaffarabad, Pakistan
2University of Engineering and Technology, Lahore, Pakistan
3King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
Keywords: cadmium sulfate, 1,3-diazinane-2-thione, crystal structure

Abstract >>
A cadmium(II) complex tetrakis(1,3-diazinane-2-thione)cadmium(II) sulfate [Cd(Diaz)4]SO4 (1) is prepared and its crystal structure is determined by X-ray crystallography. The crystal structure of 1 consists of [Cd(Diaz)4]2+ and SO42- ions. In the complex ion, the central cadmium atom is coordinated by four Diaz molecules through sulfur atoms adopting a distorted tetrahedral geometry. The molecular structure is stabilized by N-HO and N-HS hydrogen bonding interactions. The complex is also characterized by IR and NMR spectroscopy and the spectroscopic data are discussed in terms of the nature of bonding.

DOI: http://dx.doi.org/10.1134/S0022476615030099



10.
CRYSTAL STRUCTURE OF 2-[BENZYL-(7-OXO-CYCLOHEPTA-1,3,5-TRIENYL)-AMINO]-N-CYCLOHEXYLPROPANAMIDE

A. Ramazani1, S.W. Joo2, I. Amini3, K. Ślepokura4, T. Lis4, A. Souldozi1
1Islamic Azad University, Zanjan, Iran
2Yeungnam University, Republic of Korea
3Payame Noor University, Tehran, Iran
4University of Wrocław, Wrocław, Poland
Keywords: single crystal X-ray structure, smiles rearrangement, Ugi-type coupling, tropolone, cyclohexylisocyanide, benzyl amine, acetaldehyde, Ugi-Smiles-type reaction

Abstract >>
The title compound 2-[benzyl-(7-oxo-cyclohepta-1,3,5-trienyl)-amino]-N-cyclohexylpropanemide is synthesized and studied by the single crystal X-ray diffraction method. The structure of the product was confirmed by IR, 1H and 13C NMR spectroscopy, and mass spectrometry. The tropone oxygen atom plays an important role in the solid-state molecular structure stabilization by being involved in intramolecular N-H⋯O and C-H⋯O contacts.

DOI: http://dx.doi.org/10.1134/S0022476615030105



11.
CRYSTAL STRUCTURE AND DFT STUDY OF N-PHENYL-N-(PYRIDIN-4-YL)ACETAMIDE

S. Umezono, T. Okuno
Wakayama University, Sakaedani, Wakayama 640-8510, Japan
Keywords: crystal structure, DFT calculation, acetamide, pyridine, hydrogen bond

Abstract >>
The title compound N-phenyl-N-(pyridin-4-yl)acetamide (1) crystallizes in the monoclinic crystal system in the space group P21/n with unit cell parameters a = 9.097(7) Å, b = 11.824(11) Å, c = 10.128(10) Å, β = 106.64(2), V = 1043.8(16) Å3 and Z = 4. The structure of the amide unit is almost planar. The dihedral angles of the amide plane with the benzene and pyridine rings are 58.40(5) and 61.51(5) respectively, indicating that neither phenyl nor pyridyl group is conjugated with the amide unit.

DOI: http://dx.doi.org/10.1134/S0022476615030117



12.
MOLECULAR AND CRYSTAL STRUCTURE OF ISOSTEVIOL SULPHITE

B. Dobrynin, O. V. Andreeva, I. A. Litvinov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center , Russian Academy of Sciences, Kazan, Russia
Keywords: isosteviol, sulphite, X-ray crystallographic analysis, hydrogen bond

Abstract >>
The molecular and crystal structure of isosteviol sulphite (1) is studied by means of the X-ray crystallographic analysis. It is demonstrated that this compound has a dimer structure, i.e. two isosteviol molecules are bound with a sulphite bridge. The molecule takes a tweezers-like conformation stabilized by intramolecular hydrogen bonds of acid groups. The molecules in the crystal are bound by intermolecular -ͅ hydrogen bonds.

DOI: http://dx.doi.org/10.1134/S0022476615030129



13.
X-RAY SPECTROSCOPY OF CARBON-ENCAPSULATED IRON NANOPARTICLES

V. R. Galakhov1, S. N. Shamin1, M. A. Uimin1, A. E. Ermakov1, D. W. Bukhvalov2,3
1Miheev Institute of Metal Physics, Ural Branch, Russian Academy of Sciences, Ekaterinburg, Russia
2Department of Chemistry, Hanyang University, Seoul, Korea
3Theoretical Physics and Applied Mathematics Department, Ural Federal University, Ekaterinburg, Russia
Keywords: X-ray absorption spectra, photoelectron spectra, resonant inelastic X-ray scattering, carbon-encapsulated nanoparticles, Stone-Wales defects

Abstract >>
The composition and electronic structure of carbon-encapsulated iron nanoparticles Fe@C are examined by X-ray photoelectron, X-ray absorption, and resonant emission spectroscopy methods. It is found that the core in the Fe@C nanocomposite is in the metallic state with an impurity of iron carbide, which is preserved for two years. Experimentally measured spectra are compared to the calculations of the electronic structure of graphene performed at the density functional theory level. It is revealed that the Fe@C carbon shell can be presented as several graphene layers with Stone-Wales topological defects. Based on the measurements of X-ray resonant emission K a spectra of carbon, the energy band dispersion of the carbon shell of Fe@C nanoparticles is investigated and the manifestation of Stone-Wales defects in them is shown.

DOI: http://dx.doi.org/10.1134/S0022476615030130



14.
THE ELECTRONIC STRUCTURE OF COBALT COMPLEXES Co(CO)4GeCl3 AND Co[Ge(C6H5)3](CO)3[P(C6H5)3]

A. V. Maksimova1, V. G. Vlasenko1, A. V. Kozinkin1, O. V. Kulikova1, S. S. Podsukhina1, V. N. Uvarov2
1Research Institute of Physics, Southern Federal University, Rostov-on-Don, Russia
2Kurdyumov Institute for Metal Physics of the National Academy of Sciences of Ukraine, Kyiv, Ukraine
Keywords: X-ray emission spectra, density functional theory method, electronic structure, heteronuclear cobalt carbonyl complexes

Abstract >>
The electronic structure of two dinuclear heteroligand metal complexes Co(CO)4GeCl3 and Co[Ge(C6H5)3](CO)3[P(C6H5)3] with the Co-Ge bond is studied by X-ray emission spectroscopy and quantum chemical calculations at the density functional theory level. The combined analysis of the fine structure of the K b5 spectra and the calculated data makes it possible to compare the characteristics of the spectral components and to determine chemical interactions in the molecules.

DOI: http://dx.doi.org/10.1134/S0022476615030142



15.
THE ELECTRONIC STRUCTURE OF DEFECT CHALCOPYRITE CdGa2Se4 AS DETERMINED FROM FIRST PRINCIPLES CALCULATIONS AND X-RAY SPECTROSCOPY STUDIES

A. A. Lavrentyev1, B. V. Gabrelian1, P. N. Shkumat1, I. Ya. Nikiforov1, O. V. Parasyuk2, O. Yu. Khizhun3
1Don State Technical University, Rostov-on-Don, Russia
2Ukrainka Eastern European National University, Lutsk, Ukraine
3Frantsevich Institute for Problems in Materials Science, National Academy of Sciences of Ukraine, Kiev, Ukraine
Keywords: electronic structure, defect chalcopyrite, densities of states, X-ray spectrum

Abstract >>
The total and partial densities of states of all components of CdGa2Se4 are calculated using the modified ab initio augmented plane wave (APW) method implemented in the WIEN2k software package. The results of the APW calculations indicate that in the CdGa2Se4 compound, the Se states are the main contributions to the valence band, and their contribution is maximum at the top of the valence band, meanwhile at the bottom of the conduction band the contributions of the Gas* states dominate. According to the theoretical APW-calculations, the Cdd and Gap electronic states also contribute sufficiently to the valence band (mostly at the bottom and at the top of the band respectively) in CdGa2Se4. The joint alignment of CdLβ2,15, GaKβ2 and SeKβ2 X-ray emission bands and of the X-ray photoelectron spectrum of the valence electrons obtained for the CdGa2Se4 single crystal, in a common energy scale, shows good agreement of the obtained theoretical and experimental data referring to the characteristic properties of the electronic structure of the CdGa2Se4 compound.

DOI: http://dx.doi.org/10.1134/S0022476615030154



16.
X-RAY SPECTRA AND CHARGE STATES OF CATIONS IN NANOSTRUCTURED MANGANITES La0.5Ca0.5MnO3 AND Nd0.5Sr0.5MnO3

V. V. Mesilov, V. R. Galakhov, S. N. Shamin, B. A. Gizhevskii, S. V. Naumov
Miheev Institute of Metal Physics, Ural Branch, Russian Academy of Sciences, Ekaterinburg, Russia
Keywords: X-ray spectroscopy, nanostructured manganites, grinding in a vibration mill, calculations of atomic multiplets

Abstract >>
From the analysis of experimental X-ray absorption spectra and the calculation of atomic multiplets it is found that the grinding of powder manganites La0.5Ca0.5MnO3 and Nd0.5Sr0.5MnO3 in a vibration mill results in the formation of nanocrystallites and a partial transformation of trivalent manganese ions into tetravalent. It is shown that in nanostructured manganite La0.5Ca0.5MnO3 the energy gap between the occupied and unoccupied states is absent. It os found that Mn2+ ions arise in Nd0.5Sr0.5MnO3 due to more intense deformation during the grinding.

DOI: http://dx.doi.org/10.1134/S0022476615030166



17.
LOCAL ATOMIC STRUCTURE OF COPPER COMPLEXES WITH 2-TOSYLAMINOBENZYLIDENE-2'-AMINO-5'-CHLOROTHIOPHENOL

A. S. Burlov1, V. G. Vlasenko2, S. A. Mashchenko1, D. A. Garnovskii1,3, A. I. Uraev1, S. I. Levchenkov3, Ya. V. Zubavichus4, T. V. Lifintseva3
1Institute of Physical and Organic Chemistry, Southern Federal University, Rostov-on-Don, Russia
2Institute of Physics, Southern Federal University, Rostov-on-Don, Russia
3Southern Federal University, Rostov-on-Don, Russia
4National Research Center Kurchatov Institute, Moscow, Russia
Keywords: azomethines, metal chelates, XANES, EXAFS, wavelet transformation, local atomic structure

Abstract >>
A new 2-tosylaminobenzylidene-2'-amino-5'-chlorothiophenol ligand and its mono- and binuclear copper complexes are synthesized. Their structures are characterized by IR, 1 NMR, and magnetochemistry. In the copper binuclear complex there is the antiferromagnetic exchange interaction between paramagnetic centers. The dimeric structure of the copper complex is confirmed by X-ray absorption spectroscopy. The addition of pyridine to the dimeric cooper complex results in the formation of a paramagnetic monomeric structure in which pyridine is coordinated to metal via the nitrogen atom.

DOI: http://dx.doi.org/10.1134/S0022476615030178



18.
STRUCTURE OF THE GROUND AND EXCITED STATES IN THE Co2FeSi HEUSLER ALLOY ACCORDING TO THE RESONANT PHOTOEMISSION DATA

V. I. Grebennikov1,2, A. Buling3, M. Neumann3, V. V. Marchenkov1, T. V. Kuznetsova1
1Institute of Metal Physics, Ural Division, Russian Academy of Sciences, Ekaterinburg, Russia
2Ural State University of Railway Transport, Ekaterinburg, Russia
3Osnabrück University, Germany
Keywords: semimetal ferromagnetic, resonant photoemission, selective excitation of elements, X-ray spectroscopy, photohole effects, multiparticle excitations, spin polarization

Abstract >>
The electronic structure of the ground and low-energy excited states of the Co2FeSi Heusler alloy is investigated by the methods of X-ray absorption spectroscopy (XAS) and resonant X-ray photoelectron spectroscopy (RXPS). The orbital and spin magnetic moments of the iron and cobalt atoms are determined in a 0.05 T magnetic field. A comparative analysis is given of two amplifier channels of the valence band photoemission at the resonant excitation of the 2 p level: elastic and Auger electron emission. A decrease in the magnetic moment of the atom leads to a qualitative change in the resonant photoemission spectrum. The valence electron shake-up at a sudden appearance of a 2 core photohole on the iron atoms leads to multiple formations of low-energy electron-hole pairs and gives rise to continuous losses in the XPS and XAS spectra. Shake-up in the cobalt atoms with great probability gives rise to one electron-hole pair with an energy of 4 eV, which is manifested as a satellite band in the above mentioned spectra. The mentioned feautures are closely related to semimetal ferromagnetism.

DOI: http://dx.doi.org/10.1134/S002247661503018X



19.
ATOMIC AND ELECTRONIC STRUCTURE OF CdS-BASED QUANTUM DOTS

A. N. Kravtsova, M. A. Soldatov, S. A. Suchkova, V. V. Butova, A. L. Bugaev, M. B. Fain, A. V. Soldatov
Southern Federal University, Rostov-on-Don, Russia
Keywords: quantum dots, cadmium sulfide, doping, atomic and electronic structure, computer modeling, XANES spectroscopy

Abstract >>
The ab initio computer design of the CdS-based quantum dots and the cobalt doped CdS quantum dots is carried out. The characteristics features of the atomic and electronic structures of semiconductor colloidal quantum dots on CdS of different sizes are studied, and the effect of cobalt impurity atoms is estimated. We have proved the sensitivity of the X-ray absorption near-edge structure (XANES) method for the verification of the nanosized atomic structural parameters calculated by the methods of computer modeling for small-scale quantum dots of the CdS family, and for the determination of the local environment parameters of the cobalt atom in the quantum dot.

DOI: http://dx.doi.org/10.1134/S0022476615030191



20.
SIMULATION OF X-RAY EMISSION AND PHOTOELECTRON SPECTRA OF H2Pc USING THE DENSITY FUNCTIONAL METHOD

G. I. Semushkina1, L. N. Mazalov1,2,3, S. A. Lavrukhina1, T. V. Basova1, R. V. Gulyaev4
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
3Novosibirsk State Technical University, Novosibirsk, Russia
4Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: phthalocyanine, X-ray emission spectroscopy, photoelectron spectroscopy, density functional method

Abstract >>
X-ray emission and photoelectron spectroscopy and quantum chemical calculations are applied to study the electronic structure of <sub>2</sub>Pc. A comparative analysis of the experimental and theoretical data of the energy spectrum and the partial composition of HOMO for phthalocyanine is performed. It is shown that the <sub>2</sub>Pc HOMO is mainly composed of carbon 2<i>p</i><sub>p</sub>AO - gd. The best agreement between the experimental partial density distribution in HOMO and the theoretical one is observed for the calculation by the density functional method in the Z+1 approximation. The DFT-ZORA method with LB94 model functional and the QZ4P basis set enables a high-accuracy calculation of the energies of 1<i>s</i> levels of non-equivalent atoms in <sub>2</sub>Pc relative to each other.

DOI: http://dx.doi.org/10.1134/S0022476615030208



21.
AN XPS STUDY OF PRODUCTS FORMED ON Pyrite and pyrrhotine BY REACTING WITH PALLADIUM(II) CHLORIDE SOLUTIONS

A. S. Romanchenko, Yu. L. Mikhlin
Institute of Chemistry and Chemical Technology, Siberian Branch, Russian Academy of Sciences, Krasnoyarsk, Russia
Keywords: X-ray photoelectron spectroscopy, sulfide minerals, pyrite, pyrrhotine, palladium sulfides, palladium chloride complexes

Abstract >>
X-ray photoelectron spectroscopy (XPS) is used to study the products formed by reacting the main iron sulfide minerals-pyrite and pyrrhotine-with an H2PdCl4 solution (pH 2, 25 C). Palladium deposition data are obtained depending on time and the pretreatment of the surface of the minerals. Palladium is shown to be bonded as PdS sulfide nanoparticles and, to a small degree, as an adsorbed Pd(II) chloride complex. Preoxidation of the minerals has little effect on the composition of Pd-containing surface products on pyrrhotine, but on pyrite a part of Pd(II) is reduced to metal and lower sulfides. No reduced products form if oxidation results in a metal-deficient polysulfide layer on the surface.

DOI: http://dx.doi.org/10.1134/S002247661503021X



22.
ULTRAVIOLET AND X-RAY PHOTOELECTRON SPECTRA AND THE ELECTRONIC STRUCTURE OF Eu(III) AND Lu(III) β-DIKETONATE COMPLEXES

A. V. Shurygin, V. V. Korochentsev, I. S. Osmushko, A. I. Cherednichenko, V. A. Yashin, V. I. Vovna
Far Eastern Federal University, Vladivostok, Russia
Keywords: photoelectron spectroscopy, density functional theory, rare-earth element chelates, La, Eu, Lu, electronic structure

Abstract >>
Ultraviolet (UV) and X-ray photoelectron spectroscopy and quantum chemistry methods (DFT) are used to study tris-β-diketonates of the rare-earth metals europium and lutetium. New information is obtained on the electronic structure of the complexes. The geometric and electronic structures of the compounds are calculated. The nature of chemical bonding in the compounds is analyzed. The quantum-chemical studies reveal patterns in the variations of the electronic structure, which depend on the complexing agent, and determine the effects of the substitution of C(C)3 and CF3 for C 3-groups in the ligands. Band identification is obtained for the UV (in the gaseous phase) and X-ray photoelectron (in the condensed state) spectra of Eu and Lu tris-dibenzoylmetanates.

DOI: http://dx.doi.org/10.1134/S0022476615030221



23.
ELECTRONIC STRUCTURE OF NITROGEN-CONTAINING INTRACOMPLEX NICKEL(II) COMPOUNDS BASED ON ULTRAVIOLET PHOTOELECTRON SPECTRA AND DENSITY FUNCTIONAL THEORY

A. A. Komissarov, V. V. Korochentsev, V. I. Vovna
Far Eastern Federal University, Vladivostok, Russia
Keywords: nickel acetylacetoiminate, photoelectron spectra, density functional theory, electronic structure, Koopmans defect

Abstract >>
The electronic structure of nickel(II) bis-acetylacetoiminate and ethylene-bis-acetylacetoiminate is studied at the density functional theory level. Based on the quantum chemical calculations in the Koopmans theorem approximation, the bands of gas phase spectra of the studied complexes are assigned. The effect of amine substitution in nickel acetylacetonate on the character of the ligand bonding with the complexing agent is established.

DOI: http://dx.doi.org/10.1134/S0022476615030233



24.
AN XPS AND TPD STUDY OF GOLD OXIDE FILMS OBTAINED BY EXPOSURE TO RF-ACTIVATED OXYGEN

A. I. Stadnichenko1,2, S. V. Koshcheev1, A. I. Boronin1,2
1Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research University, Novosibirsk, Russia
Keywords: gold oxide, adsorbed oxygen, gold, surface, XPS, TPD, plasma, oxide film

Abstract >>
Low-temperature oxidation of the polycrystalline surface of bulk metallic gold with radio-frequency activated oxygen is used to obtain oxide films, which are investigated by a combination of X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD). The XPS estimate for the composition and thickness of the oxide films is close to Au2O3 and is 6-10 nm. The analysis of the Au4f and O1s lines reveals only one state of the oxidized gold, which is described by Eb(Au4 f ) = 85.5 eV, and two nonequivalent states of oxygen with Eb(O1s ) = 529.3 eV and 530.3 eV, which are uniformly distributed over the oxide film and may be attributed to nonequivalent oxygen states in the gold oxide structure. The thermal stability study shows that the gold oxide decomposes in one stage into metal at a temperature of Tdes = 530 K. According to the TPD data, the desorption activation energy is Edes = 140 kJ/mol. The high-temperature oxidation of the gold surface reveals the formation of dissolved oxygen in bulk gold. This oxygen is characterized by a broad TPD peak with a maximum at Tdes = 800 K. This oxygen state is not detected by XPS. The concentration of dissolved oxygen is supposed to be below the XPS sensitivity threshold and is estimated at about 1% or less.

DOI: http://dx.doi.org/10.1134/S0022476615030245



25.
FILMS OF THE Pdx Ce1 xO2 SOLID SOLUTION AS A MODEL OBJECT FOR THE XPS STUDY OF THE SURFACE CHEMISTRY OF Pd/CeO2 CATALYSTS

R. V. Gulyaev1,2, D. Yu. Osadchii1,2, S. V. Koscheev1, A. I. Boronin1,2
1Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: palladium, ceria, solid solution, catalysts, low-temperature oxidation of CO, photoelectron spectroscopy, films, deconvolution

Abstract >>
The paper demonstrates a new technique for preparing nanostructured films of the PdxCe1xO2xδ solid solution. The obtained films are similar to real powder catalysts by their chemical and structural properties and are conductive, which is favorable for the XPS methoda. The effect of the CO+O2 reaction on the oxidized and reduced surfaces is studied using these model objects. The presence of the reversible PdxCe1xO2x δ ↔ surface palladium forms transition occurring already at room temperatures in the CO+O2 reaction is shown. Deconvolution of the O1s spectra made it possible for the first time to separate experimentally the contributions from OH hydroxyl and CO32 carbonate surface groups.

DOI: http://dx.doi.org/10.1134/S0022476615030257



26.
CALCULATION OF THE PURE SURFACE COMPOSITION OF THE BINARY ALLOY ACCORDING TO XPS DATA OBTAINED AFTER THE ALLOY SURFACE CONTACT WITH AIR

Z. Kh. Kalazhokov1, B. S. Karamurzov1, A. G. Kochur2, L. B. Misakova1, Z. V. Kardanova1, Kh. Kh. Kalazhokov1
1Berbekov Kabardino-Balkarian State University, Nalchik, Russia
2Rostov State Transport University, Rostov-on-Don, Russia
Keywords: surface, electron spectrometer, free path, elemental composition, alloy, contaminations, surface layer, photoemission, adsorption film

Abstract >>
An XPS technique to determine the surface concentrations of the components of binary alloy prepared in an ultra-high vacuum chamber and subjected to the contact with the air is proposed. The technique takes into account the effect of the adsorption film on the sample surface, which distorts the photoelectron current of the analytical XPS lines. The potential of the technique is demonstrated by the example of studying Sn-Pb system alloys.

DOI: http://dx.doi.org/10.1134/S0022476615030269



27.
SYNTHESIS AND STRUCTURE OF TETRASODIUM ITRILTRISMETHYLENEPHOSPHONATO ZINCATE TRIDECAHYDRATE Na4[ZnN(CH2PO3)3]13H2O, A CORROSION INHIBITOR

F. F. Chausov1, E. A. Naimushina1, I. N. Shabanova2, N. V. Somov3
1Udmurt State University, Izhevsk, Russia
2Institute of Physics and Technology, Ural Branch, Russian Academy of Sciences, Izhevsk, Russia
3Lobachevsky State University of Nizhni Novgorod, Nizhni Novgorod, Russia
Keywords: corrosion inhibitor, coordination compounds, zinc, organophosphonate complex, nitriltrismethylenephosphonate, intramolecular coordination, chelate complexes

Abstract >>
Organophosphonate zincate corrosion inhibitor (CCDC 919565) contains the Zn-N bond closing three five-membered chelate rings with the formation of a common bonding electronic subsystem of N-Zn-O-P atoms. Zinc is coordinated in a distorted trigonal bipyramidal configuration involving the oxygen atom of the neighboring molecule of the complex. Space group P1(-), Z = 2, a = 11.2208(2) Å, b = 11.2666(3) Å, c = 12.3286(3) Å, α = 108.455(2), β = 97.168(2), γ = 117.103(2). The inhibitor does not form polymeric structures, provides the stability and reproducibility of technological quality parameters. The initial decomposition temperature is 250 C. The corrosion inhibition factor is 14.3 (GOST 9.502-82, steel grade 20, medium No. 2, static conditions, natural aeration, 10 days exposure).

DOI: http://dx.doi.org/10.1134/S0022476615030270



28.
MECHANISM OF CONJUGATE ELECTRON TRANSITIONS ON THE SURFACE OF A SOLID

A. R. Cholach, V. M. Tapilin
Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: electron spectroscopy, threshold excitation, conjugate electron transitions, platinum

Abstract >>
The conjugate electron excitation (CEE) above the core-level thresholds of substrate atoms is a combination of the known electronic shake-off and shake-up electron transitions resulting in the location of excited electrons can at both vacuum level and vacant states near the Fermi level. The CEE satellites in elastic electron spectra provide the direct experimental data on the valence state structure of surface atoms and components of the adsorbed layer. The CEE control can be implemented as an additional option of the standard equipment for electron spectroscopy.

DOI: http://dx.doi.org/10.1134/S0022476615030282



29.
EFFECTS OF THE NEAREST-NEIGHBOR ENVIRONMENT OF COPPER ATOMS ON THE XANES SPECTRA OF LAYERED CHROMIUM-COPPER DISULFIDES

E. V. Korotaev1, M. M. Syrokvashin1, N. N. Peregudova1, V. V. Kanazhevskii2,3, L. N. Mazalov1,2, V. V. Sokolov1
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
3Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: layered chromium-copper disulfides, crystals, XANES, finite difference method, multiple scattering method

Abstract >>
In the present work, the K absorption spectra of copper, chromium, and vanadium of layered chromium-copper disulfides CuCr1xVxS2 (x = 00.4) are studied. Based on the comparison of the experimental and theoretical spectra obtained by simulation with the FDMNES program package, it is shown that copper atoms occupy tetrahedral sites, and chromium atoms and substitutional vanadium atoms occupy octahedral sites in the whole set of the samples studied.

DOI: http://dx.doi.org/10.1134/S0022476615030294