Activation diffusion of oxygen under conditions of the metal-semiconductor phase transition in vanadium dioxide

Density functional theory is used to calculate the energies of formation of oxygen vacancies and migration of oxygen in the monoclinic and rutile phases of vanadium dioxide. The results are compared to estimates of the parameters of activation diffusion of oxygen using data from the electron-beam modification of thin film structures of vanadium dioxide and their subsequent reduction in the temperature range of 20–100°C. It is shown that diffusion in both phases of vanadium dioxide has a preferential direction of oxygen migration along axis а in the monoclinic phase and axis с in the rutile phase. The difference between the rate of oxygen vacancy generation upon electron-beam exposure above and below the temperature of metal–semiconductor phase transition is explained by the jump (~150%) in the activation energy of oxygen diffusion upon the structural transition of rutile–monoclinic phase. The mobility of oxygen (oxygen vacancies) correspondingly changes by more than an order of magnitude.     

Photoinduced oxygen adsorption of AgBr crystals at 77 K

Photoinduced adsorption (PIA) of oxygen molecules on AgBr films at 77 K has been experimentally observed and investigated. Lifetimes of PIA centers and desorption activation energies of O₂ molecules have been determined. The process is suggested to compete with the ionic step of AgBr photolysis.

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- () - AgBr 77 K. - O₂. , , - AgBr.

     

Charged particle activation analysis for surface oxygen under various ambient pressures

Charged particle activation analysis has proved to be useful for the determination of surface oxygen under any atmospheric conditions. The¹⁶O(³He, p)¹⁸F reaction was used for activation. The sample in a form of two plates was contacted intimately with each other and bombarded with³He particles of such an energy as to give the maximum cross section at the inside surfaces of the plates. The¹⁸F thus formed in the forward plate was then measured. Oxygen in the gap between the two plates can be shown to cause no noticeable interference. This method was applied to silicon, aluminium and lead in four different ambient pressures.     

Kinetics and rate-limiting mechanisms of dolomite dissolution at various CO2 partial pressures

Techniques of rotating-disk and catalyst were used in investigating the kinetics of dolomite dissolution in flowing CO₂-H₂O system. Experiments run in the solutions equilibrated with various CO₂ partial pressures (P_{CO 2} ) from 30 to 100000 Pa. It shows that dissolution rates of dolomite are related with rotating speeds at conditions far from equilibrium. This was explained by modified diffusion boundary layer (DBL) model. In addition, the dissolution rates increase after addition of carbonic anhydrase (CA) to solutions, where the CA catalyzes CO₂ conversion. However, great differences occur among various CO₂ partial pressures. The experimental observations give a conclusion that the modified DBL model enables one to predict dissolution rates and their behaviour at various P_{CO 2} with satisfactory precision at least far from equilibrium.     

Kinetics and rate-limiting mechanisms of dolomite dissolution at various CO_2 partial pressures

Techniques of rotating-disk and catalyst were used in investigating the kinetics of dolomite dissolution in flowing CO2-H2O system. Experiments run in the solutions equilibrated with various CO2 partial pressures (PCO2) from 30 to 100000 Pa. It shows that dissolution rates of dolomite are related with rotating speeds at conditions far from equilibrium. This was explained by modified diffusion boundary layer (DBL) model. In addition, the dissolution rates increase after addition of carbonic anhydrase (CA) to solutions, where the CA catalyzes CO2 conversion. However, great differences occur among various CO2 partial pressures. The experimental observations give a conclusion that the modified DBL model enables one to predict dissolution rates and their behaviour at various PCO2 with satisfactory precision at least far from equilibrium.     

Long-wavelength fluorescent indicators for the determination of oxygen partial pressures

A series of stable heterocyclic indicators with λ_ex = 469–566 nm and λ_em = 511–652 nm allows the fluorimetric determination of ca. 1–100% partial pressures of oxygen by quenching of fluorescnce, especially in toluene solution.     

Raman spectroscopy of nacrite single crystals at 298 and 77 K

A Raman microscope in conjunction with a thermal stage has been used to determine the Raman spectra of single crystals of nacrite at 298 and 77 K. The spectra obtained are a function of the physics of the spectrometer and were orientation dependent. Bands are observed at 3710, 3646, 3630 and 3623 cm(-1). Upon obtaining the Raman spectra at liquid nitrogen temperature, the band at 3648 cm(-1) was not observed but an additional band at 3603 cm(-1) appeared. This latter band may be attributed to the hydroxyl stretching of non-hydrogen bonded interlayer hydroxyls in the nacrite. The bands attributed to both the inner and inner surface hydroxyls moved to lower frequencies upon cooling to liquid nitrogen temperatures. Low frequency bands also showed orientation dependence.     

The elastic properties of hexatriacontane single crystals at their various phase transitions

For the first time directly measured elastic tensor components of C₃₆H₇₄ single crystals are presented as a function of temperature. The data are compared to theoretical results obtained for polyethylene.     

Phase stability of BSCF in low oxygen partial pressures

In situ X-ray diffraction has been used to investigate the phase stability of barium strontium cobalt iron oxide (BSCF) with the formula Ba_0.5Sr_0.5Fe_1−xCo_xO_3−δ (x=0, 0.2, 0.4, 0.6, 0.8, and 1). The thermal decomposition processes in both low partial pressures of oxygen (air −10⁻⁵ atm pO₂) and in reducing conditions have been detailed. BSCF manifests excellent stability down to 10⁻⁵ atm pO₂; however, it decomposes through a complex series of oxides under reducing conditions. Increasing the cobalt content results in a decrease in the temperature range of stability of the material under 4% H₂ in N₂, with the initial decomposition taking place at 375, 425, 550, 600, 650 and 675 °C, for x=1, 0.8, 0.6, 0.4, 0.2 and 0, respectively. Further, the thermal expansion is a strong function of the oxygen activity and Co content. The x=0, 1 end member, BSC, undergoes a phase transition from rhombohedral to cubic symmetry at ∼800 °C under 10⁻⁵ atm pO₂, resulting in an ideal perovskite with a=3.9892(3) Å at room temperature.     

Determination of oxygen in bismuthate single crystals

An improved procedure for determining oxygen in single crystals was developed. The procedure was tested on samples prepared from stoichiometric BaBiO₃ by thermal treatment in a controlled medium. The error of the procedure is about 0.5 mol%.     

Phase and chemical transformations in the SiO2-Fe2O3(Fe3O4) system at various oxygen partial pressures

The SiO₂-Fe₂O₃(F₃O₄) system has been studied in air, oxygen, and an inert atmosphere. The dissociation temperatures for iron oxides, the onset and full melting temperatures for coexisting phases, and the melt demixing temperatures have been determined as a function of the oxygen partial pressure. A scenario of the phase and chemical transformations in the title systems has been developed.     

Behavior under gamma irradiation of single crystals of NaCl doped with divalent cations

Thermally stimulated luminescence and optical absorption measurements were performed on NaCl single crystals, both single and double doped. The NaCl single crystals were exposed to gamma rays from a ⁶⁰Co source at both low and room temperatures. The radiation-induced defects were mainly F and H centers, and the absorption bands for the F centers were centered at 464 nm. Bleaching with F-light showed the participation of the F center generated by gamma radiation on the TL phenomenon. The results suggest that NaCl single crystals, both single and double doped can be used as dosimeters, within certain doses.     

Kinetics and rate-limiting mechanisms of dolomite dissolution at various CO2 partial pressures

Techniques of rotating-disk and catalyst were used in investigating the kinetics of dolomite dissolution in flowing CO₂-H₂O system. Experiments run in the solutions equilibrated with various CO₂ partial pressures (P_{CO 2} ) from 30 to 100000 Pa. It shows that dissolution rates of dolomite are related with rotating speeds at conditions far from equilibrium. This was explained by modified diffusion boundary layer (DBL) model. In addition, the dissolution rates increase after addition of carbonic anhydrase (CA) to solutions, where the CA catalyzes CO₂ conversion. However, great differences occur among various CO₂ partial pressures. The experimental observations give a conclusion that the modified DBL model enables one to predict dissolution rates and their behaviour at various P_{CO 2} with satisfactory precision at least far from equilibrium.     

Identification of primary free radicals in trehalose dihydrate single crystals X-irradiated at 10 K

Primary free radical formation in trehalose dihydrate single crystals X-irradiated at 10 K was investigated at the same temperature using X-band Electron Paramagnetic Resonance (EPR), Electron Nuclear Double Resonance (ENDOR) and ENDOR-induced EPR (EIE) techniques. The ENDOR results allowed the unambiguous determination of six proton hyperfine coupling (HFC) tensors. Using the EIE technique, these HF interactions were assigned to three different radicals, labeled R1, R2 and R3. The anisotropy of the EPR and EIE spectra indicated that R1 and R2 are alkyl radicals (i.e. carbon-centered) and R3 is an alkoxy radical (i.e. oxygen-centered). The EPR data also revealed the presence of an additional alkoxy radical species, labeled R4. Molecular modeling using periodic Density Functional Theory (DFT) calculations for simulating experimental data suggests that R1 and R2 are the hydrogen-abstracted alkyl species centered at C5' and C5, respectively, while the alkoxy radicals R3 and R4 have the unpaired electron localized mainly at O2 and O4'. Interestingly, the DFT study on R4 demonstrates that the trapping of a transferred proton can significantly influence the conformation of a deprotonated cation. Comparison of these results with those obtained from sucrose single crystals X-irradiated at 10 K indicates that the carbon situated next to the ring oxygen and connected to the CH(2)OH hydroxymethyl group is a better radical trapping site than other positions.     

Kinetics of the disproportionate of N-arylhydroxylamines at different hydrogen partial pressures

Conclusions Dependence of the reaction rate on the hydrogen partial pressure 400–150 hPa, was noted in the disproportionate of N-arylhydroxylamines in the presence of a platinum catalyst in a hydrogen-nitrogen atmosphere. This dependence is attributed to the increase in the amount of oxygen-containing products, which are strongly adsorbed on the catalyst and inhibit the reaction. At hydrogen pressures above 0.1 MPa, oxygen-containing products are not formed and the rate of disproportionation is not dependent on the hydrogen pressure.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2844–2846, 1988.The authors express their gratitude to V. G. Dorokhov for assistance in carrying out these experiments.     

Radiation products at 77 K in trehalose single crystals: EMR and DFT analysis

The radicals obtained in trehalose dihydrate single crystals after 77 K X-irradiation have been investigated at the same temperature using X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and ENDOR-induced EPR (EIE) techniques. Five proton hyperfine coupling tensors were unambiguously determined from the ENDOR measurements and assigned to three carbon-centered radical species (T1, T1*, and T2) based on the EIE spectra. EPR angular variations revealed the presence of four additional alkoxy radical species (T3 to T6) and allowed determination of their g tensors. Using periodic density functional theory (DFT) calculations, T1/T1*, T2, and T3 were identified as H-loss species centered at C4, C1', and O2', respectively. The T4 radical is proposed to have the unpaired electron at O4, but considerable discrepancies between experimental and calculated HFC values indicate it is not simply the (net) H-loss species. No suitable models were found for T5 and T6. These exhibit a markedly larger g anisotropy than T3 and T4, which were not reproduced by any of our DFT calculations.