Quasiresonance charge exchange of hydrogen isotopes mesic atoms in excited states

Processes of charge exchange of hydrogen isotopes mesic atoms in excited states at low collision energies 10^?2?E?1 eV are studied. The cross sections calculated depend on energy like ～E ^?1 and are of an order of the atomic cross sections (～10^?16 cm²). It is shown that the high rates (～10¹² s^?1) of charge exchange and thermalization of mesic atoms in excited states at the liquid hydrogen density are comparable with the rates of cascade transitions in mesic atoms.     

Electron attachment to oxygen and oxygen/ozone clusters studied in a high-resolution crossed beams experiment

Highly monochromatized electrons (with 30 meV FWHM) are used in a crossed beams experiment to investigate electron attachment to oxygen clusters (O₂)_n at electron energies from approximately zero eV up to 2 eV. At energies close to zero the attachment cross section for the reaction (O₂)_n +e → O ₂ ^? varies inversely with the electron energy, indicative of s-wave electron capture to (O₂)_n. Peaks in the attachment cross section present at higher energies can be ascribed to vibrational levels of the oxygen anion. The vibrational spacings observed can be quantitatively accounted for. In addition electron attachment to mixed oxygen/ozone clusters has been studied in the energy range up to 4 eV. Despite the initially large excess of oxygen molecules in the neutral clusters the dominant attachment products are undissociated cluster ions (O₃) _m ^? including the O ₃ ^? monomer while oxygen cluster ions (O₂) _n ^? appear with comparatively low intensity.     

Mechanisms of oxygen adsorption and desorption on polycrystalline palladium

The adsorption and desorption of oxygen on a polycrystalline palladium (Pd(poly)) surface (10-to 100-μm crystallites; ～32% (100), ～18% (111), ～34% (311), and ～15% (331)) at P _O2 ≤ 1.3 × 10^?5 Pa and T = 500–1300 K have been studied by TPD and mathematical modeling. The kinetics of O₂ adsorption and desorption on Pd(poly) are primarily governed by the formation and decomposition of oxygen adsorption structures on the (100) and (111) crystallite faces. The O₂ adsorption rate is constant at ? ≤ 0.15–0.25 owing to the formation of the p(2 × 2) structure with an O_ads-surface bonding energy of D(Pd-O) = 364 kJ/mol on the (100) and (111) faces. The adsorption rate decreases with increasing coverage at ? ≥ 0.15–0.25 because of the growth, on the (100) face, of the c(2 × 2) structure, in which D(Pd-O) is reduced to 324 kJ/mol by lateral interactions in the adsorption layer. A high-temperature (～800 K) O₂ desorption peak is observed for ? ≤ 0.25, which is due to O₂ desorption from a disordered adsorption layer according to a second-order rate law with an activation energy of E _des = 230 kJ/mol. A lower temperature (～700 K) O₂ desorption peak is observed for ? ≥ 0.25, which is due to O₂ released by the c(2 × 2) structure according to a first-order rate law with E _des = 150 kJ/mol. At ? ≥ 0.25, there are repulsive interactions between O_ads atoms on Pd(poly) (ε_aa = 5–10 kJ/mol).     

Spin dependence of low energy charge exchange between H 2 + and Na

The difference in charge exchange rate in collisions between spin oriented sodium atoms and H ₂ ⁺ ions has been measured at an energy of about 1 eV. H ₂ ⁺ was stored in a Penning trap and polarized by spin exchange with Na beam atoms from a hexapole magnet. The ion loss from the trap due to charge exchange was different as we depolarized the atomic beam. From the data we obtain a ratio of cross sections for singlet and triplet collisionsQ ₁/Q ₃=1.5±0.2 andQ ₃=1.2·10^?15 cm².     

The nature of molecular oxygen binding and activation in Mn-O2 complex

Non-empirical calculations of CASSCF energies, electric dipole moments, Einstein coefficients, matrix elements of the operator of spin-orbital interaction between states of different multiplicity in a model complex ^6,8[Mn-O₂] of C _2v symmetry have been made in 3-21G, 6-31G, 6-31G** basis sets. The crosssections of the potential energy surface (PES) of the ground and excited states were built. It is found that oxygen bonding to manganese is possible when excited atoms of manganese collide with molecular oxygen, singlet oxygen with Mn[⁶ S _5/2] atoms, or in a close contact O₂[X³Σ _g ^? ] + Mn[⁶ S _5/2] and is determined by charge transfer states ^6,8CTS(Mn⁺O ₂ ^? ). Mechanisms of singlet oxygen activation/deactivation are determined by a considerably increased probability of electric dipole transitions b ¹Σ _g ⁺ ?a ¹Δ_g, a ¹Δ_g?X³Σ _g ^? , b ¹Σ _g ⁺ ?X³Σ _g ^? induced in oxygen in the collision process.     

Dynamic computer simulations of Cs incorporation in Si during low‐energy (0.2–3 keV) irradiation

The incorporation of Cs atoms in silicon was investigated by dynamic computer simulations using the Monte‐Carlo code T‐DYN that takes into account the gradual change of the target composition due to the Cs irradiation. The implantation of Cs atoms at normal incidence was studied for four energies (0.2, 0.5, 1, and 3 keV) and three different Cs surface‐binding energies U_Cs (0.4, 0.8, and 2.4 eV). The total implantation fluences were 2 × 10¹⁷ Cs cm^?2 for 0.2 keV, 1.5 × 10¹⁷ Cs cm^?2 for 0.5 keV, and 1 × 10¹⁷ Cs cm^?2 for 1 and 3 keV. At these values, a stationary state has been reached. The steady‐state Cs‐surface concentrations exhibit a pronounced dependence both on impact energy and U_Cs, varying between ～1 (at 0.2 keV and U_Cs = 2.4 eV) and ～0.13 (3 keV and U_Cs = 0.4 eV). Under equilibrium, the partial sputtering yield of Si, Y_Si, experiences little influence of U_Cs, but varies with the Cs energy: at U_Cs = 0.8 eV from 0.09 to 1.0 Si atoms/Cs projectile. For all irradiation conditions a strongly preferential sputtering of Cs atoms as compared to Si atoms is found, increasing from 1.8 (at 3 keV and U_Cs = 2.4 eV) to 13.3 (at 0.2 keV and U_Cs = 0.4 eV). Preferential sputtering of Cs increases with decreasing irradiation energy and decreasing U_Cs. Copyright © 2008 John Wiley & Sons, Ltd.     

EPR studies of isotopic exchange involving adsorbed oxygen species on MgO

In the EPR spectra of ¹⁷O₂^? adsorbed on MgO, the hyperfine lines due to ¹⁷O(I = $\text{5}\text{2}$) have been used to monitor the isotopic exchange with gas phase oxygen. The predicted behaviour of the different possible mechanisms (place exchange and/or isotopic exchange) is compared with the experimental results which show that, on MgO at room temperature, isotopic exchange occurs via an intermediate species which is tentatively identified as O₄^?.     

Oxygen adsorption on nickel surfaces: Detection of different species by x-ray photoelectron spectroscopy

Interaction of oxygen with evaporated nickel films has been studied by X-ray photoelectron spectroscopy, XPS, over the temperature range 77–500 K and pressure range 10^?9?10^?4 torr. Three oxygen species have been positively identified from O(1s) binding energy shifts (I, II and III with BE's 529.5, 531.4 and 533.2 eV). A fourth state at ca. 534.8 eV may also exist. The relative proportions of each species present depends on the temperature of the substrate. Type I is tentatively considered to represent oxygen atoms in an oxide-like electronic environment, type II is assigned as chemisorbed oxygen atoms, although the possibility of assignment at high oxygen coverages to a defect Ni₂ O₃ structure is admitted. Type III is only formed in sub-monolayer quantities on interaction at 77 K; converting irreversibly to II on warming to 300 K. I and II are always formed together between 300 and 500 K. The authors believe this implies some incorporation of oxygen atoms from the start of adsorption, which in turn has important implications for recent LEED studies.     

Displacement of metal atoms from salts by hydrogen and the role of this reaction in chain processes

The interaction of hydrogen atoms with a variety of alkali metal and alkaline-earth metal salts results not only in the recombination of these atoms but also in the displacement, into the gas phase, of free radicals (CaCl^·(A ¹ P _1/2, B ² S ⁺) and CaF^·(A ² P)) and metal atoms, including their excited species, which are detected spectroscopically. Transmission spectra indicate that the NaCl surface undergoes metallization when treated with a high-frequency discharge and a rarefied hydrogen flame. Combustion is affected by the gas-phase hydrogen atoms involved in the chain reaction and by the varying composition and properties of the surface. The concentration of Na atoms over the NaCl surface at 770 K is 10⁹?10¹¹ cm^?3 in a stream of H atoms at 1 Torr and in the 2H₂ + O₂ flame at 4 Torr. The concentration of sodium atoms in the ² P _3/2 and ² P _1/2 excited states is ～5 × 10⁶?5 × 10⁸ cm^?3. The role of the discovered reactions in combustion, pyrolysis, and plasma chemistry is discussed.     

Infrared spectroscopic evidence of the Mg3O3 molecule formed by reaction of magnesium and oxygen atoms in inert gas matrices at 20.4°K

The reaction of magnesium and oxygen atoms in argon, krypton, xenon and oxygen matrices at 20.4° K was studied by infrared spectroscopy between 200 and 4000 cm^?1. The appearance of a band in the magnesium-oxygen stretching region, reproducible in all the matrices, indicates that reaction takes place. Oxygen-13 isotopic substitution suggests that the absorption is due to Mg₃O₃, whose formation is supported by the crystal structure of the solid phase. The force constants are calculated as f_R = 2.3 mdyne/Å and F_?/R² = 0.44 mdyne/Å assuming a planar six-membered ring of alternate magnesium and oxygen atoms with bond angles O-Mg-O 100° and Mg-O-Mg 140°.     

Kinetic study of electronically excited silicon atoms,Si(3p2(1S0)), by time-resolved attenuation of atomic resonance radiation

The collisional behaviour of electronically excited silicon atoms in the 3p²(¹S₀) state, 1.909 eV above the 3p²(³P₀) ground state, is investigated by time-resolved attenuation of atomic resonance radiation at λ = 390.53 nm (4s(¹P^o₁)←3p² (¹S₀)). The optically metastable Si(3¹S₀) atoms were generated by the repetitive pulsed irradiation of SiCl₄ and their decay monitored in the presence of added gases. Absolute quenching rate constants (k_Q, cm³ molecule^?1 s^?1, 300 K) are reported for the following collision partners: He (?1.3 × 10^?15), SiCl₄ ((9.1 ± 1.4) × 10^?11), O₂ ((1.5 ± 0.2) × 10^?11) and N₂O ((4.3 ± 0.4) × 10^?11). The results for O₂ and N₂O are compared with analogous data reported hitherto for Si(3p²(³P_J)) and with those for the other np²(¹S₀) states of the group IV atoms C, Ge, Sn and Pb. The rate data for the silicon atoms are considered in terms of the nature of the potential surfaces arising from symmetry arguments based on the weak spin orbit coupling approximation.     

Improved activity of SnO for the photocatalytic oxygen evolution

SnO prepared by soft chemistry exhibits a black color and semiconducting properties. The X-ray diffraction indicates a tetragonal symmetry (SG: P4/nmm) with nano crystallites of an average size of 85 nm. The forbidden band, determined from the diffuse reflectance is found to be 1.46 eV. The electrical conductivity occurs by polaron hopping and follows an Arrhenius type law with activation energy of 0.21 eV, the change in the slope at 526 K is attributed to the oxidation to SnO₂. The photo-electrochemical study shows n type conduction with a flat band potential of ?0.45 V, close to the photocurrent onset potential (?0.40 V). The electrochemical impedance spectroscopy shows the bulk contribution of SnO (R_b = 1.7 kΩ cm²) and decreases down to 1.89 kΩ cm² under illumination. The photocatalytic properties have been evaluated for the first time for to the oxygen evolution. The valence band, deriving from Sn²⁺: 5p orbital with a potential (?0.80 V_SCE/5.55 eV), is suitably positioned with respect to O₂/H₂O level (～0.6 V_SCE), leading to water oxidation under visible light. The best performance occurs at pH ～ 7 with an oxygen liberation rate of 23 µmol mL h^?1 (mg catalyst)^?1 and a quantum efficiency of 1.2%. An improvement of ～13% is observed on the system SnO/clay.     

Electrochemical and kinetic study of oxygen in a perfluorotributylamine emulsion

Oxygen can be determined in a perfluorotributylamine emulsion used as a blood substitute by coulometry and polarography. The oxygen uptake of the emulsion (4.3 × 10^?3 mol l^?1 or 11 ml-% at 25°C and P_O2 = 760 mm Hg) is about three times greater than that of water. The adsorption of surfactant on a dropping mercury electrode changes the electrochemical parameters E_{$\text{1}\text{2}$}, α and k₃. The marked difference between the diffusion coefficients of oxygen and hydrogen peroxide (ratio 2.6) seems to be proceed from the ejection of oxygen molecules from the perfluorotributylamine droplets and from the insolubility of hydrogen peroxide molecules in the droplets. The constant rate of oxygen release by these droplets was estimated to be 10⁴ s^?1 by a stopped-flow spectrophotometric method. This constant rate seems to be linked with the particle diameter (0.2 μm) and the diffusion coefficient in the perfluorotributylamine droplets (1.6 × 10^?6 cm² s^?1).     

Energy transfer in collisions of Ar(3P0,2 metastable atoms with H(2S) atoms. I. Total rate constant and mechanism

The Ar(4s,³P₂) + H(1S,²S) reaction, which gives excited H(n=2) atoms, has been studied. The room temperature rate constant for Lyman-α (2p-1s) excitation was measured as 2.4 × 10^?10 cm³ mol^?1 s^?1. The method was based upon comparison of the Lyman-α emission intensity with the Kr resonance emission intensity produced from Ar(³P₂) + Kr, which has a known rate constant. The H atom excitation, which has a large energy defect of 1.3 eV, is discussed in terms of a curve crossing mechanism.     

The reactions of methyl radicals with atomic and molecular oxygen

The reaction of methyl radicals with atomic and molecular oxygen was studied with a photoionization mass spectrometer. The methyl radicals were generated by reacting oxygen atoms with ethylene in a fast-flow tube reactor. The rate constant for the reaction of methyl radicals with oxygen atoms was (1.0 ± 0.2) × 10^?10 cm³/molec · sec with no significant variation with temperature over the range of 259–341°K. The reaction of methyl radicals with molecular oxygen involves both a two-body reaction, having a rate constant \documentclass{article}\pagestyle{empty}\begin{document}$\begin{array}{*{20}c} {k_{{\rm 3a}} = (10^{- 12.54 \pm 0.35})\exp [(- 940 \pm 250)T^{- 1}]} & {{\rm cm}^{\rm 3} /{\rm molec} \cdot {\rm sec}} \end{array}$\end{document} and a three-body recombination having a negative temperature dependence. The methyl peroxy radical could be observed at its steady-state concentration. The rate constants determined at low pressures are compatible with the values determined at higher pressures by flash photolysis. Formaldehyde appears to be a major product of the two-body reaction of CH₃ with O₂, and also of the reaction of CH₃O₂ with oxygen atoms.     

Study of the reactions of oxygen atoms with carbonothioicdichloride,carbonothioicdifluoride, and tetrafluoro-1,3-dithietane

The reactions of ground-state oxygen atoms with carbonothioicdichloride, carbonothioicdifluoride, and tetrafluoro-1,3-dithietane have been studied in a crossed molecular jet reactor in order to determine the initial reaction products and in a fast-flow reactor in order to determine their overall rate constants at temperatures between 250 and 500 K. These rate constants are??(O + C₂CS) =(3.09 ± 0.54) × 10^?11 exp(+115 ± 106 cal/mol/RT),??(O + F₂CS) = (1.22 ± 0.19) × 10^?11 exp(-747 ± 95 cal/mol/RT), and??(O + F₄C₂S₂) = (2.36 ± 0.52) × 10^?11 exp(-1700 ± 128 cal/mol/RT) cm³/molec˙sec. The detected reaction products and their rate constants indicate that the primary reaction mechanism is the electrophilic addition of the oxygen atom to the sulfur atom contained in the reactant molecule to form an energy-rich adduct which then decomposes by C-S bond cleavage.     

T-x diagram and transport properties of the GeSe-GeI2 solid electrolyte

The T-x diagram for the GeSe-GeI₂ system was plotted based on DTA, XRD, and conductivity data. The diagram features a simple eutectic and a limited region of solid solutions with prevalent GeSe content. It was established that, in the region of solid solutions, the properties of the GeSe-GeI₂ solid electrolyte are substantially dependent on the concentration of the GeI₂ dopant. The highest conductivity (10^?3?10^?4 S/cm at 150°C), lowest activation energy of electric conduction (0.3–0.4 eV), and lowest electronic (hole) transport numbers (10^?5?10^?7 at 150°C) at high ionic (～1.0) and cationic (0.9–1.0) transport numbers were observed at a GeI₂ concentration of 3–6 mol %. In the two-phase region, the transport properties (conductivity and activation energy of conduction) only slightly depend on the dopant concentration.     

Mechanism of Framework Oxygen Exchange in Fe‐Zeolites: A Combined DFT and Mass Spectrometry Study

The role of framework oxygen atoms in N₂O decomposition [N₂O(g)→N₂(g) and 1/2O₂(g)] over Fe‐ferrierite is investigated employing a combined experimental (N₂¹⁸O decomposition in batch experiments followed by mass spectroscopy measurements) and theoretical (density functional theory calculations) approach. The occurrence of the isotope exchange indicates that framework oxygen atoms are involved in the N₂O decomposition catalyzed by Fe‐ferrierite. Our study, using an Fe‐ferrierite sample with iron exclusively present as Fe^II cations accommodated in the cationic sites, shows that the mobility of framework oxygen atoms in the temperature range: 553 to 593 K is limited to the four framework oxygen atoms of the two AlO₄^? tetrahedra forming cationic sites that accomodate Fe^II. They exchange with the Fe extra‐framework ¹⁸O atom originating from the decomposed N₂¹⁸O. We found, using DFT calculations, that O₂ molecules facilitate the oxygen exchange. However, the corresponding calculated energy barrier of 87 kcal mol^?1 is still very high and it is higher than the assumed experimental value based on the occurrence of the sluggish oxygen exchange at 553 K.     

Crystal structure and high-temperature electrical conductivity of novel perovskite-related gallium and indium oxides

Novel complex oxides Sr₂Ga_1+x In_1?x O₅, x?=?0.0–0.2 with brownmillerite-type structure were prepared in air at T?=?1,273 K, 24 h. Study of the crystal structure of Sr₂Ga_1.1In_0.9O₅ refined using X-ray powder diffraction data (S.G. Icmm, a?=?5.9694(1) Å, b?=?15.2091(3) Å, c?=?5.7122(1) Å, χ ²?=?2.48, R _F ²? ₌?0.0504, R _p?=?0.0458) revealed ordering of Ga³⁺ and In³⁺ cations over tetrahedral and octahedral positions, respectively. A partial replacement of Sr²⁺ by La³⁺ according to formula Sr_1?y La _y Ga_0.5In_0.5O_2.5+y/2, leads to the formation of a cubic perovskite (a?=?4.0291(5) Å) for y?=?0.3. No ordering of oxygen vacancies or cations was observed in Sr_0.7La_0.3Ga_0.5In_0.5O_2.65 as revealed by electron diffraction study. The trace diffusion coefficient (D _T) of oxygen for cubic perovskite Sr_0.7La_0.3Ga_0.5In_0.5O_2.65 is in the range 2.0?×?10^?9–6.3?×?10^?8 cm²/s with activation energy 1.4(1)?eV as determined by isotopic exchange depth profile technique using secondary ion mass spectrometry at 973–1,223 K. These values are close to those reported for Ca-doped ZrO₂. High-temperature electrical conductivity of Sr_0.7La_0.3Ga_0.5In_0.5O_2.65 studied by AC impedance was found to be nearly independent on oxygen partial pressure. Calculated values of activation energy at T?<?1,073 K for hole and oxide-ion conductivities are 0.96 and 1.10 eV, respectively.     

The diffusion of oxygen and ion transport in lanthanum cobaltite LaCoO<Subscript>3-δ</Subscript>

The chemical diffusion coefficient of oxygen vacancies and oxygen ion conductivity in lanthanum cobaltite LaCoO₃ were determined by the polarization method as functions of oxygen partial pressure \(p_{O_2 } \) (atm) and temperature T(K) over the ranges ?4 ≤ log \(p_{O_2 } \) ≤ 0 and 1173 K ≤ T ≤ 1323 K. The mobilities (cm²/(V s)) of oxygen vacancies calculated over the temperature range studied satisfy the inequalities 1.8 × 10^?5 ≤ \(v_{v_0 } \) ≤ 3.4 × 10^?5. The transfer numbers of oxygen vacancies were calculated. These numbers change depending on oxygen partial pressure over the range 5 × 10^?7 ≤ t ₀ ≤ 1 × 10^?5. The activation energy of self-diffusion of oxygen vacancies was found to be E _a= 104 ± 10 kJ/mol (1.1 ± 0.1 eV).