Home – Home – Jornals – 2015 number 8

Thermodynamic analysis of experimental data has demonstrated that FeO activity in silicate melts identical in composition to natural magmas can be described by the regular-solution model, which takes into account interactions of all cations with Si and interaction of Ca with Al. Using this model, we propose an oxygen barometer for spinel + magma phase association. In contrast to the earlier proposed methods for estimation of oxygen chemical potential, this barometer can work in the PT-domain close to the liquidus of magmatic process. The new oxygen barometer has been applied to magmas related to mantle plume activity, including Siberian meimechites, Hawaiian picrites, and picrites from the Emeishan large igneous province (LIP) and Greenland. We have shown that most magmas related to the activity of deep-seated mantle plumes are characterized by a higher relative chemical potential of oxygen than magmas of mid-ocean ridges. Thermodynamically calculated stability fields of rocks with different carbon-containing phases show that under PT-conditions of the lower mantle, the material of ascending mantle plumes is characterized by relatively elevated oxygen fugacity. Formation of diamond in the lower mantle requires more oxidizing conditions as compared with the major part of this geosphere, where the presence of Fe-Ni alloy is predicted. We have put forward a hypothesis that the main reason for the oxygen fugacity increase in particular domains of the lower mantle is a shift of redox equilibria toward a decrease in the amount of Fe-Ni alloy, up to its disappearance, with temperature growth.

This paper discusses the genesis of large Siberian alkaline massifs hosting major ore deposits. These reference massifs are grouped based on the predominance of alkalies (K or Na) and their agpaitic index (miaskitic and agpaitic). We proposed new emplacement schemes for the Tomtor, Murun, Burpala, Synnyr, and Bilibino massifs supported by petrochemical and geochemical data, as well as new age estimates. Types of their ore potential and genesis of rare-metal mineralization are discussed. The formational types of carbonatites as the main ore-bearing rocks are given. The depth of magma generation and types of mantle sources are determined using isotopic data from previous studies. A model of plume-related generation of ultramafic alkaline magmas is proposed.

Despite the violent eruption of the Siberian Traps large igneous province at ~250 Ma, the Siberian craton has an extremely low heat flow (18-25 mW/m²) and a very thick lithosphere (300-350 km), which makes it an ideal place to study the influence of mantle plumes on the long-term stability of cratons. Compared with seismic velocities of rocks, the lower crust of the Siberian craton is composed mainly of mafic granulites and could be rather heterogeneous in composition. The very high v_P (>7.2 km/s) in the lowermost crust can be fit by a mixture of garnet granulites, two-pyroxene granulites, and garnet gabbros as a result of magma underplating. The high-velocity anomaly in the upper mantle ( v_P = 8.3-8.6 km/s) can be interpreted by a mixture of eclogites and spinel peridotites. Combined with the study of lower crustal and mantle xenoliths, we recognized multistage magma underplating at the crust-mantle boundary beneath the Siberian craton, including the Neoarchean growth and Paleoproterozoic assembly of the Siberian craton beneath the Markha terrane, the Proterozoic collision along the Sayan-Taimyr suture zone, and the Triassic Siberian Trap event beneath the central Tunguska basin. The Moho becomes a metamorphism boundary of mafic rocks between granulite facies and eclogite facies rather than a chemical boundary that separates the mafic lower crust from the ultramafic upper mantle. Therefore, multistage magma underplating since the Neoarchean will result in a seismic Moho shallower than the petrologic Moho. Such magmatism-induced compositional change and dehydration will increase viscosity of the lithospheric mantle and finally trigger lithospheric thickening after mantle plume activity. Hence, mantle plumes are not the key factor for craton destruction.

Magmatism of the Uda sector enclosed within the West Transbaikalian rift zone (WTRZ) is discussed in this paper. Seven stages of the Late Mesozoic-Cenozoic volcanism have been recognized within span 174-51 Ma. On the border about 135 Ma the nature of volcanism changed noticeably: (a) the volume of volcanic rocks essentially reduced; (b) transition from differentiated to basaltic associations proceeded with the disappearance of volcanics containing SiO2 over 54 wt.%; (c) alkali and subalkaline basaltoids appeared in the associations, their volume increasing at later stages. Geochemical features of the Uda volcanics are determined by participation in their formation of the mantle source close in composition to the source with OIB parameters. They are responsible for high concentrations of incompatible elements in magmatic products. The isotope characteristics of rocks indicate conformity of this mantle source to the varying behavior of EMII and PREMA with the role of the latter strengthening in time. The basaltoids of initial stages show the deficit of Ti, Nb, and Ta caused by involvement of water-saturated lithosphere mantle in magma formation. The main specifics of the Uda volcanics composition and the pattern of their variability in time correspond to those in WTRZ, as well as in the other Late Mesozoic-Cenozoic rift zones of Central Asia. This evidence suggests similar geodynamic settings for origination and development of rifting processes, when continuously evolving mantle plume affects the regional lithosphere. The magmatism of the Uda sector, as in the entire WTRZ, differs considerably from magmatic processes developing over the convergent boundaries of the Mongol-Okhotsk belt; their products are represented by differentiated magmatic associations with geochemical properties are common for the rocks of suprasubduction zones.

New data on geology, geochemistry, and isotope systematics of lavas in the East Sikhote-Alin area, along with earlier published evidence for the Sea of Japan, provide insights into the dynamics of back-arc basins and their role in the tectonic and magmatic history of continental margins. Right-lateral strike-slip faulting, the key event in the Cenozoic history of East Sikhote-Alin, apparently had no relation with the subduction in post-Eocene time. At that time, the Late Cretaceous subduction ended and oceanic asthenosphere with Pacific-type MORB isotope signatures injected into the subcontinental mantle through slab windows. The Sea of Japan opening began in the Eocene with formation of small rift basins in the Tatar Strait, which accumulated coastal facies. During the main Miocene phase of activity, the zone affected by oceanic asthenosphere moved eastward, i.e., to the modern deepwater Sea of Japan. The effect of oceanic asthenosphere on the continental margin ended in the Late Miocene after the Sea of Japan had opened and new subduction initiated east of the Japan Islands.

The paper presents new data on age, geochemistry, and Sr and Nd isotope composition of rocks from the Akatui massif and comagmatic rocks from the lower unit of the Kailas Formation (Akatui volcanoplutonic association), localized within the Aleksandrovskii Zavod depression. The amphibole 40Ar/39Ar age date the monzogabbro of the early phase of the Akatui massif at 154.8 ± 4.4 Ma; the monzonite of the main phase yields a 40Ar/39Ar age of 160.7 ± 3.9 Ma, and the shoshonite basalt of the lower unit of the Kailas Formation yields a 40Ar/39Ar age of 161.5 ± 1.7 Ma. The leading petrogenetic mechanism for the Akatui volcanoplutonic association is crystal fractional differentiation of melts with minor crustal contamination, which can be suggested from the mineralogical and petrographic features and geochemical and isotope characteristics of rocks. The geochemical data for the Akatui volcanoplutonic association show LILE, LREE, U, Th, and Pb enrichment with a characteristic depletion in high-field strength elements (HFSE), such as Nb and Ti. They are also depleted in P. Sr-Nd isotope data (87Sr/86Sr_{(160 Ma)} = 0.70642-0.70688 and εNd(160 Ma) = -0.6 to -2.2) suggest an EMII-type mantle source and could also indicate a negligible degree of crustal contamination in the evolved melts.

We present results of a comparative study of Late Paleozoic granitoids of Eastern Kazakhstan and Western Transbaikalia composing the large Kalba-Narym and Angara-Vitim batholiths. We have established that despite the different geologic history of these regions, granitoid magmatism there proceeded nearly synchronously at the Carboniferous-Permian boundary (330-280 Ma) and was accompanied by mantle magmatism. The regularities of its evolution are considered in terms of the plume model and different stages of interaction of mantle plumes with the lithosphere. The major principles of plume-lithosphere interaction in accretion-collision fold belts have been formulated: (1) Plume-lithosphere interaction results in large-scale melting of sublithospheric mantle, lower lithosphere, and crustal substrates warmed by the preceding orogenic process; (2) The processes last 30 to 50 Myr and produce large volumes of igneous rocks, mostly granitoids; (3) The sequence of formation of granitoid and basic igneous complexes and the metallogenic specialization can be different and depend on the lithosphere structure and preceding geologic history of the region.

We provide new isotope-geochronological evidence for the synchronous occurrence of Late Paleozoic basic and granitoid magmatism in Western Transbaikalia; this is a strong argument for the contribution of mantle magmas to granitoid petrogenesis. The Late Paleozoic basic rocks originated from the phlogopite-garnet-bearing lherzolitic mantle, which melted under «hydration conditions». The specific features of Late Paleozoic magmatism in Western Transbaikalia were determined by the combination of the activity of a low-energy mantle plume with the final stage of the Hercynian orogeny in space and time. At the early stage of magmatism, during the formation of the Barguzin granites, the plume had only a thermal influence on the crustal rocks heated as a result of Hercynian fold-thrust deformations. The mixing of mantle basic and crustal salic magmas at different levels marked the transition from crustal to mixed (mantle-crustal) granites, which include all post-Barguzin complexes (probably, except for alkali granites). In the geologic evolution of Transbaikalia, the Late Paleozoic magmatism was postorogenic, but it was initiated and influenced by the mantle plume.

We have revealed the spatio-temporal regularities of distribution of platinum group elements (PGE) in basaltoids related to the activity of the Siberian mantle plume. As objects of study, we chose rift and flood basalts from the Norilsk district (sampled from the SD-9 borehole), flood basalts from the central part of the Tunguska syneclise (Lower Tunguska), Kuznetsk Basin traps, and subalkalic basalt from the Semeitau volcanoplutonic structure in eastern Kazakhstan. Based on the PGE patterns of basaltoids related to the activity of the Permo-Triassic Siberian plume, we have shown that the rocks that formed in the central part of the Siberian Large Igneous Province (LIP) at the early rift stage have low contents of PGE, whereas picrites and tholeiitic flood basalts have high contents. The rift (Semeitau structure) and flood (Kuznetsk Basin traps) basalts from the peripheral regions are characterized by extremely low PGE contents. The high PGE contents in magmas of the plume head are responsible for the high productivity of ultramafic-mafic trap magmatism. The elevated K contents in magmas and the high PGE contents in the mantle plume head are probably due to the assent of deep-seated material from the core-lower-mantle boundary, as follows from the thermochemical model of the Siberian plume.

This study aims at summarizing available geological and geochemical data on known Proterozoic platinum-bearing ultramafic-mafic massifs in the south of Siberia. Considering new data on geochemistry and geochronology of some intrusions, it was feasible to compare ore-bearing complexes of different time spans and areas and to follow their relationships with the recognized large igneous provinces. In the south of Siberia, the platinum-bearing massifs might be united into three age groups: Late Paleoproterozoic (e.g., Chiney complex, Malozadoisky massif), Late Mesoproterozoic (e.g., Srednecheremshansky massif), and Neoproterozoic (e.g., Kingash complex, Yoko-Dovyren massif, and massifs in the center of the East Sayan Mts.). In most massifs but Chiney the initial magmas are magnesium-rich. On paleogeodynamic reconstructions, the position of the studied massifs is the evidence that three most precisely dated events in North Canada continued into southern Siberia: In the period 1880-1865 Ma, it was the Ghost-Mara River-Morel LIP; at 1270-1260 Ma, the Mackenzie LIP; and at 725-720 Ma, the Franklin LIP. In Siberia, the mostly productive massifs with respect to PGE-Ni-Cu mineralization are those linked with the Franklin LIP: Verkhnii Kingash, Yoko-Dovyren, and central part of the Eastern Sayan Mountains, e.g., Tartay, Zhelos, and Tokty-Oy.

Lavas in Alexandra Land Island of the Franz Josef Land Archipelago bear Au-Cu-Pd-type mineralization. The found mineral species belong to the Cu-Au-Pd and Pd-Cu-(Te + Sb + S + As) systems being, respectively, (i) cuproauride (Au(Cu, Pd)) and auricupride (Au(Cu,Pd)3) and (ii) phases similar to skaergaardite (PdCu), nielsenite (PdCu3), and numerous S-Te-Sb-Pd-Cu phases of various compositions. The morphology of PGM existing as tiny grains and films along the boundaries of plagioclase and clinopyroxene and in cracks, their crystallization at low temperatures predicted by experimental data, and the presence of native copper with sulfur impurity are signatures of postmagmatic origin. The Alexandra Land tholeiitic basalts and dolerites were, most likely, produced by the hotspot which may be the source of PGE-bearing intrusions in eastern Greenland that contain PGM similar to those discussed in the paper.

The review presents the main results of the studies of Prof. S. P. Gabuda, which were devoted to the NMR investigation of the mobility of atoms and molecules. The basic principles of his model for averaging local magnetic fields under the conditions of atomic and molecular mobility are outlined. This model provides a relationship between the parameters of these fields with the structural features of the mobility of atoms and molecules and intermolecular interactions. Ionic and molecular crystals, zeolites, molecular sieves, hydrated proteins, and so on are considered. Phase transitions in guest subsystems, effects of dynamic disordering and correlated electron motion on the mobility of atoms and molecules and their location are discussed.

The review presents the experimental and theoretic data on relativistic effects in solids, which were the objects of S. P. Gabuda’s studies. Coordination and cluster compounds are considered. Unique data obtained by nuclear magnetic resonance, vibrational spectroscopy, magnetochemistry and other methods are presented. The possibilities of the occurrence of polymorphic phase transitions, the Jahn-Teller effect, intermolecular interactions, and other effects due to the features of structure of relativistic wave functions are discussed.

Understanding the behaviour of solid solutions over wide ranges of temperature and pressure remains a major challenge to both theory and experiment. Here we report a detailed exchange Monte Carlo study using a classical ionic model of the model perovskite parascandolaite-neighborite (K,Na)MgF₃ solid solution and its end-members for temperatures in the range 300-1000 K and pressures from 0-8 GPa. Full account is taken of the local environment of the individual cations, clustering and thermal effects. Properties considered include the crystal structure, phase transitions, the thermodynamics of mixing and the non-ideality of the solid solution. Clustering of the potassium ions is examined via a short-range order parameter. Where experimental data are available for comparison, agreement is very good.

Structures and relative energies of binuclear iron-manganese complexes with the phosphine ligand L, which exist in vinylidene Cp(CO)(L)MnFe(m-C=CHPh)(CO)₄ (2) and benzylidene ketene h⁴-{C[Mn(CO)(L)Cp]××(CO)CHPh}Fe(CO)₃ (3) forms are calculated by the B3LYP density functional method. Four isomers with different positions of ligand L relative to the phenyl ring (conformers a and b) and the substituent Ph relative to the С=С bond (conformers E and Z) are considered for each form and their relative stability is determined. It is shown that all isomers of 2 have approximately the same energy (within 4 kcal/mol) whereas the energies of isomers of 3 differ within 21 kcal/mol. Isomer 3Ea in which the PPh₃ ligand contacts with the phenyl substituent of the vinylidene group is most energetically favorable. It is found that with an increase in the L ligand size in the order PH₃ < PH₂Ph < PHPh₂ < PPh₃ the Mn-P bond length increases to 2.37 Å in the most stable isomer of form 3 and to 2.43 Å in the isomers of 2 and three conformers of 3. A more substantial increase in the Mn-P bond length in complexes 2 and 3 correlates with their lower stability as compared to isomer Ea of 3, which is consistent with experimental data on the presence of only one conformer 3Ea in solution.

Within the density functional theory the electronic structure of triple molybdates Li₂M₃Al(MoO₄)₄, where M = Cs, Rb, is studied for the first time. It is found that all molybdates studied belong to wide band insulators with a band gap of ~4 eV. Quadrupole frequencies and asymmetry parameters of the electric field gradient near magnetic ⁷Li, ²⁷Al, ⁸⁷Rb, and ¹³³Cs nuclei are calculated and experimental NMR spectra are interpreted.

Using density functional theory the electronic structure, chemical bond parameters, phase formation energies, and intrinsic defects in metal and non-metal sublattices of chalcogenides MX₂ (M = Nb, Mo, W; X = Se, Te) are determined. For compounds with X = Te a monotonic decrease in charges on metal and non-metal atoms occurs with increasing atomic number, however, for compounds with X = Se this order is violated. With increase in the metal atomic number for both selenides and tellurides, the formation energies increases, i.e. the stability of these phases decreases. The formation energies of vacancies in both sublattices of these systems have a non-monotonic character. For MX₂ (M = Mo, W; X = Se, Te) systems the formation of vacancies in the chalcogen sublattice results in the semiconductor-metal transition, and vacancies in the metal sublattice decrease the band gap.

The B3LYР/6-31( p , d ) density functional method is applied to pheromones of the forest xylophagous insects Ips typographus L. , Monochamus urussovi Fisch ., and Monochamus galloprovincialis Oliv . to calculate the absorption spectra and find excited states. The calculated results are used to assess the possible activity of the molecules when they are affected by solar radiation.

Stacking faults along the (111) direction in low-temperature metastable aluminum oxide (η-Al₂O₃ and χ-Al₂O₃) are studied using density functional theory (DFT). The surface energy of Al₂O₃ (111) is calculated; the intermediate layer between crystalline domains is considered; the ²⁷Al nuclear quadrupole coupling constants are determined.

We review the properties of simple diatomic molecular glasses as explored by nuclear magnetic resonance techniques and measurements of the dielectric susceptibility. We focus on the behavior of classical molecular rotors formed by solid N₂-Ar mixtures and discuss the time dependent behavior in terms of replica symmetry breaking theories.

We report solid-state ³⁵Cl NMR spectra in three hexachlorides, (NH₄)₂SeCl₆, (NH₄)₂TeCl₆ and Rb₂TeCl₆. The C_Q (³⁵Cl) quadrupole coupling constants in the three compounds were found to be 41.4±0.1 MHz, 30.3±0.1 MHz and 30.3±0.1 MHz, respectively, some of the largest C_Q (³⁵Cl) quadrupole coupling constants ever measured in polycrystalline powdered solids directly via ³⁵Cl NMR spectroscopy. The ³⁵Cl EFG tensors are axial in all three cases reflecting the C _{4 v} point group symmetry of the chlorine sites. ³⁵Cl NMR experiments in these compounds were only made possible by employing the WURST-QCPMG pulse sequence in the ultrahigh magnetic field of 21.1 T. ³⁵Cl NMR results agree with the earlier reported ³⁵Cl NQR values and with the complementary plane-wave DFT calculations. The origin of the very large C_Q (³⁵Cl) quadrupole coupling constants in these and other main-group chlorides lies in the covalent-type chlorine bonding. The ionic bonding in the ionic chlorides results in significantly reduced C_Q (³⁵Cl) values as illustrated with triphenyltellurium chloride Ph₃TeCl. The high sensitivity of ³⁵Cl NMR to the chlorine coordination environment is demonstrated using tetrachlorohydroxotellurate hydrate K[TeCl₄(OH)]×0.5H₂O as an example. ¹²⁵Te MAS NMR experiments were performed for tellurium compounds to support ³⁵Cl NMR findings.

The mobility of water molecules in natural natrolite (Na₂Al₂Si₃O₁₀×2H₂O) is investigated by the ¹H NMR method. The spin-lattice relaxation times in the laboratory and rotating frames ( T ₁ and T _1r) are measured as a function of the temperature for a polycrystalline sample. From experimental T ₁ data it follows that at T > 286 K the diffusion of water molecules along channels parallel to the c axis is observed. From experimental T _1r data it follows that at T > 250 K the diffusion of water molecules in transversal channels of natrolite is also observed. At a low temperature ( T < 250 K) the dipolar interaction with paramagnetic impurities (presumably Fe³⁺ ions) becomes significant as a relaxation mechanism of ¹H nuclei.

Solid-state ¹H NMR is applied to investigate the kinetics of diffusion of H₂O molecules in the fibrous zeolite natrolite [Na₂Al₂Si₃O₁₀]×2H₂O. It is found that the stepwise heating of the zeolite in air leads to the following pattern of molecular diffusion jumps: at first they increase in number and then decrease exponentially with time. Conducting such an experiment in an aqueous medium leads to the opposite effect. The results obtained confirm our previous suggestion about the importance of interstitial defects, or over-hydrated local states, in molecular diffusion.

The ionic mobility and conductivity in the crystalline phases of PbSnF₄- x CaF₂ systems ( x = 2.5 mol.%, 5 mol.%, 7.5 mol.%, and 10 mol.%) in the temperature range of 150-500 K are studied by NMR and impedance spectroscopy. The parameters of ¹⁹F NMR spectra, types of ion motions, and ionic conductivity in the PbSnF₄ compound doped with calcium fluoride are found to be determined by the temperature and concentration of calcium fluoride. The specific conductivity of the crystalline phases in the PbSnF₄-CaF₂ systems is rather high at room temperature, and hence, one cannot exclude the possibility to use them for the creation of functional materials with a high ionic (superionic) conductivity.

Fluorophosphatometallates with the composition K₃H₃Zr₃F₃(PO₄)₅, Rb₃H₃Zr₃F₃(PO₄)₅, Rb₃H₃Hf₃F₃(PO₄)₅, CsH₂Hf₂F₂(PO₄)₃×2H₂O are studied by ³¹P, ¹⁹F, and ¹H NMR. It is found that protons enter in the composition of hydrophosphate groups and fluorine atoms occupy the terminal sites in the tetravalent metal environment. Schemes of the crystal structure of fluorophosphatometallates are proposed. It is established that in CsH₂Hf₂F₂(PO₄)₃×2H₂O water molecules are bonded to the phosphate group proton via a strong hydrogen bond and are characterized by a low energy barrier of molecular motions.

A comparative structural study of LiMPO₄ (M = Mn, Fe, Co, Ni) orthophosphates and Li₂MPO₄F (M = Co, Ni) fluorophosphates obtained by mechanochemically assisted solid-state synthesis is performed using powder XRD, IR, and NMR spectroscopy methods. It is shown that all compounds crystallize in the orthorhombic symmetry (space group Pnma ). Lattice parameters decrease on passing from Mn to Ni, which is due to the decrease in the ionic radius of the d metal. According to the IR spectroscopy data, in this series an increase in the covalency of the P-O bond is observed along with a decrease in the covalency of the M-O bond. On passing to fluorophosphates, the symmetry of PO₄ tetrahedra increases. ⁶Li and ³¹P NMR spectra of all compounds are characterized by the dependence of the contact shift on the nature of metal M and the degree of distortion of the MO₆ coordination polyhedron. ⁶Li MAS NMR line width is noticeably affected by the concentration of structural defects. Unlike orthophosphates with equivalent lithium ions, fluorophosphates contain lithium ions in three different positions.

The ²⁷Al, ¹H MAS NMR method is used to study initial nanosized metastable aluminum oxides of a pseudoboehmite series (g- and d-Al₂O₃) after being coated with graphene (С@Al₂O₃) and annealed in the air (С@Al₂O₃-Т). It is demonstrated that aluminum nanoparticles coated with graphene and annealed at high temperatures (to 750°C for g and 1180°C for d) preserve their phase composition but differ from initial oxides by a very low concentration of defects (ОН groups). After the annealing of the graphene coating the hydroxyl cover of oxides is reduced, however, the set of ОН groups differs greatly from that of the initial oxides. Only one type of terminal ОН groups with a ~0.2 ppm shift and one type of bridging m²-ОН groups with a 1.8 ppm shift for g-Al₂O₃ from OH-m²-Al_VAl _n and 2.1 ppm for d-Al₂O₃ OH-m²-Al_IVAl _n are observed. The data obtained make it possible to characterize in detail the d-Al₂O₃ pure phase.

Distributions described by the Bloembergen-Rowland (BR) formula and widely used in NMR of solids for studying polycrystalline samples, which is closely connected with the problem of constructing the convolutions of such distributions with a broadening symmetric function, are strictly area normalized. The application of the obtained methodological results is illustrated by the example of the analysis of NMR data for UF₆.

The temperature and concentration dependences of ²⁰⁷Pb NMR chemical shifts of Pb(NO₃)₂ in D₂O are reported. The results are analyzed in terms of exchange between a solvated lead ion and the Pb(NO₃)⁺ contact-ion pair. Predictions of the chemical shift difference between the aquated ion and contact-ion pair are carried out for the gas-phase entities and for the solvated species with a DFT calculation. Previously reported data on ²⁰⁷Pb NMR chemical shifts of Pb(NO₃)₂ in H₂O are reevaluated. From the analysis, the enthalpy of dissociation of the contact-ion pair is found to be -42.3±1.0 kJ/mol.

Quantum chemical calculations of the [Mo₃S₇(Et₂dtc)₃](Et₂dtc) complex in different solvents are performed. It is shown that the binding energy between the cluster [Mo₃S₇(Et₂dtc)₃]⁺ cation and the outer-sphere (Et₂dtc)^- anion exponentially decreases with increase in the solvent dielectric permittivity. By DOSY NMR it is determined that in chloroform, the cationic and anionic moieties of the complex form an associate (contact ion pair), while in strongly polar dimethyl sulfoxide these moieties move independently of one another.

Optical and magneto-optical properties of solutions of crude oil of different origin (i.e., taken from different fields) are studied in the visible and near-UV region of optical emission. Magnetic circular dichroism (MCD) spectra of oil are obtained in the vicinity of wavelengths of ~410 nm, 533 nm, and 576 nm. It is demonstrated that the intensity of the MCD signal depends on the origin of crude oil, and it is proportional to the oil concentration in the solution. The comparison of the magneto-optical spectroscopy data with the chemical composition of samples allows us to conclude that the observed magneto-optical activity is determined by the presence of VO²⁺ complexes in the oil samples studied. The revealed magneto-optical activity of conventional oil can form a basis of a new method for the analysis of the composition and properties of oil of different origin.

It is considered practically impossible to differentiate between oxygen and fluorine atoms by X-ray diffraction in disordered structures of oxyfluoride compounds due to the similarity of their ionic radii and diffusion factors. Indeed, many transition metal oxyfluoride compounds containing polar pseudo-octahedral MO _x F_{6- x} ( x = 1-3) anions form crystal structures without any fluorine-oxygen (F/O) ordering owing to a large number of local anion configurations. Because of this static disorder, it is impossible to determine the positions of O and F atoms and find the real geometry of the polyhedron. However, this becomes possible in the case of dynamic disorder of oxyfluoride anions when the central atom is displaced from the center of the octahedron toward a vertex, edge, or face (depending on the number of oxygen atoms in the polyhedron), which enables the identification of O and F atoms owing to inherent differences between M-O and M-F bonding. On cooling, such compounds undergo phase transitions of the order-disorder type with substantial changes in the entropy. The examples of static and dynamic orientational disorder in oxyfluoride compounds of d ⁰ transition metals are given.

The reasons for the preference of glide planes in natural crystals are considered by studying the results of an X-ray crystallography analysis of the minerals salzburgite, eldragonite, izoklakeite, and vikingite. The glide planes organize the combination of right- of atomic fragments, which appear during crystallization, and contribute to a uniform distribution of atoms in complex compositions and a more dense and symmetrical packing. The fact that the structures have cation and anion sublattices with similar dimensions and orientations creates a situation similar to that of beats in oscillatory systems and, hence, modulates the intensity of X-ray reflections. The progressively increasing number of structures where individual atomic positions are occupied by two or more types of atoms suggests a stable geometry of the corresponding atomic sublattices with respect to compositional variations. Analysis of these “skeletal” sublattices is a key to understanding the solid-phase transformations, contact interactions, and dynamic processes in mineral associations.

The Rietveld method is used to determine the structure of two samples of high-hydrated zeolite paranatrolite: {Na_1.15Ca_0.38Sr_0.04(H₂O)_3.1}[Al_2.19Si_2.81O₁₀] (Vishnevye Mountains, Urals) and {Na_2.01K_0.04H_0.04(H₂O)_3.8}[Al_2.10Si_2.90O₁₀] (Kirov Mine, Khibiny Massif). Paranatrolite from the Vishnevye Mountains is characterized by the presence of split water positions and a relatively low total H₂O content. Local water-cation assemblages (WCAs) of three configurations are identified in the statistical “mixture”. The extraframework subsystem in the structure of Khibiny paranatrolite is made of WCAs of one configuration. The H₂O content of this mineral is close to the maximum possible amount and is a record-breaker for natrolite-type minerals.

The inclusion compound of the composition [Zn₂(dmf)(bdc)(lac)]×[Mn(C₅H₅)(CO)₃] (C₅H₅ = cyclopentadienyl) is obtained by keeping a mixture of crystals of a porous homochiral metal-organic polymer of the composition [Zn₂(dmf)(bdc)(lac)]×DMF (DMF = N,N¢-dimethylformamide, H₂bdc = terephthalic acid, H₂lac = S -lactic acid) with the excess of cymantrene at 100°C, and the crystal structure of this compound is determined.

Based on the hypothesis advanced by S. P. Gabuda that the SiO₂ molecule could undergo a transition from the linear form to the isomeric form with a ring-shaped (bent) structure, an idea is proposed that when the mantle substance melts, a phase transition of the bent SiO₂ form into the linear SiO₂ form can occur in the lower mantle. This phase transition might be of great importance for the lower-mantle convection processes and also for the rise of mantle plumes carrying both heat energy, and broad range of platinum group and rare elements to the Earth surface.

The bibliometric and subject analysis of the scientific heritage of Professor S. P. Gabuda is carried out using the national (RSCI) and international (CAPlus, WoS, and Scopus) databases.

Within density functional theory the structure of an inclusion compound based on Ni(II) dimethylglyoxymate and the macrocyclic cucurbit[8]uril nanocavitand is investigated and the thermodynamic parameters of its formation are estimated. Based on the results obtained a prediction is made about the principal possibility of the synthesis of this inclusion compound.

Using quantum chemical calculations, we report structures, energetics, natural bond analysis, aromaticity and ¹⁴N NQR parameters of the irdidapyridine isomers. The mpw1pw91, PBEPBE and PBE1PBE calculations indicate the most stability for meta-isomer. Global electrophilicity index shows that iridapyridines are stronger electrophile rather than pyridine. Local reactivity descriptors as Fukui functions, local softnesses and electrophilicity indices analyses are performed to find out the reactive sites within molecules. Nucleus-independent chemical shift (NICS) has been evaluated to understand the aromaticity. Also, changes in ¹⁴N NQR parameters of the molecules are studied.

The structures and properties of asymmetric heterocycles (HBrBN₃)_n (n = 1-4) are systematically studied at the B3LYP/6-31G* level. The molecules (HBrBN₃) _n (n = 2-4) have the core structures of a 2n-membered ring with alternating boron and a-nitrogen atoms. The relationships between geometrical parameters and oligomerization degree n are discussed. The calculated IR spectra have four main characteristic regions. Trends in thermodynamic properties with temperature and oligomerization degree n are discussed. Thermodynamic analysis of the gas-phase oligomerizations shows that formation of the most stable heterocycles (HBrBN₃)_n (n = 2-4) is enthalpy driven in the range of 200-800 K.