The predissociation of the 2σ u −1 (c 4Σ u − , v states of the oxygen molecular ion

The dynamics of predissociation of the 2σ _u ^?1 (c ⁴Σ _u ^? ), v vibrational states of the O ₂ ⁺ ion was studied theoretically using the method of coupled differential equations. The main equations describing the vibrational motions of nuclei in the adiabatic and diabatic approximations are given. The applicability scope of approximate methods for solving these equations was studied. The predissociation widths for the v = 0 and 1 vibrational levels were found to be Γ₀ = 0.054 meV and Γ₁ = 9.71 meV. This substantiated the results of recent observations of neutral fragments formed after the dissociation of the O₂ molecule. About 99% of the O ₂ ⁺ ions in the 2σ _u ^?1 (c ⁴Σ _u ^? ), v states were found to decompose to the O(¹ D) + O⁺(⁴ S) dissociation products.     

Statistical mechanism of the formation of the energy spectra of sputtered molecular clusters

The energy spectra of Si _n O _m ^? clusters sputtered from Si targets by Xe⁺ ions with O₂ pumping onto a bombarded surface, as well as by O ₂ ⁺ ions, are studied. It is shown that the form of the Si _n O _2n+1 ^? energy distributions does not depend on the experimental conditions. Significant differences in the energy spectra of O and Si monomers as compared to Si _n O _2n+1 ^? clusters are revealed. The mentioned features of the energy distribution of Si _n O _m ^? clusters are explained within the framework of the statistical recombination mechanism of their formation in combinatorial synthesis processes.     

Investigation of photoionization and photodissociation of an oxygen molecule by the method of coupled differential equations

The photoionization and photodissociation of an oxygen molecule are investigated theoretically by the method of coupled differential equations. The molecular orbitals of the core are calculated in the MO LCAO approximation. The molecular orbitals of a photoelectron in the discrete and continuous spectra are determined by the single-center method. The wave functions of vibrational motion of the oxygen molecule are obtained within the diabatic approach. The described method is used for calculating the predissociation and autoionization widths of the 2σ _u ^?1 (c ⁴Σ _u ^? )n/σ_g, v Rydberg states of the oxygen molecule. The total cross sections of the resonant photoionization and neutral predissociation calculated for the oxygen molecule in the excitation energy range 20.6–24.8 eV are in good agreement with the available experimental data.     

Mass spectrometer studies of the ion composition in the pink afterglow

The time dependences of the ion number densities in the pink afterglow of nitrogen, as represented by the ion wall currents, have been measured. The ions were extracted through an orifice from a flow system and analysed by a quadrupol mass spectrometer. It has been found thatN ₂ ⁺ ions are dominating in the early afterglow. With the beginning of the ionization processN ₃ ⁺ and at pressure >6 TorrN ₄ ⁺ become the majority ions. The ratio of the number densities(N ₃ ⁺ )/(N ₂ ⁺ ) reaches a maximum during the increase of the ionization processes before the maximum is reached. This behaviour suggestsN ₃ ⁺ ions to be the primary ions created by the ionization processes. The time dependences of the ion number densities (N ₂ ⁺ ), (N ₃ ⁺ ) and(N ₄ ⁺ ) are found to vary similar, showing that the ions are strongly coupled by conversion processes. The conversion processes are discussed. In the maximum of ionization at a total pressure of 4.4 Torr the ratios of the number densities of the afterglow ions (N ₂ ⁺ )∶(N ₃ ⁺ )∶(N ₄ ⁺) are 1∶1.9∶0.64.     

Xα-SW-calculation of the chemically induced decay constant variation of Tc-99m in the tetrahedral oxy-complex ion and the octahedral halogen-complex ions

The tetrahedral and octahedral complex ions TcO ₄ ^? , TcCl ₆ ^2? , TcBr ₆ ^2? , TcI ₆ ^2? , which exhibit experimentally determined decay constant variations of Tc-99m [1], meet the conditions for the application of the X_α-SW-method. The results of the calculations are given, including the case of TcF ₆ ^2? . The decay constant variations are evaluated using the one-electron functions in a partial-wave expansion. The results are compared with the measured values and a detailed discussion gives a comprehensive picture of the decay constant variation induced by the chemical surroundings considered.     

Pulse ENDOR studies on the radical pair P 700 +· A 1 ·− and the photoaccumulated quinone acceptor A 1 ·− of photosystem I

The secondary acceptor A₁ of the electron transport chain(s) of photosystem (PS) I is a phylloquinone (vitamin K₁, VK₁). Pulse electron paramagnetic resonance and electron nuclear double resonance (ENDOR) experiments at X-band frequencies were performed on the photoaccumulated acceptor radical A ₁ ^·? and the radical pair state P ₇₀₀ ^·+ A ₁ ^·? in PS I ofThermosynechococcus elongatus. The data obtained were compared with data from the respective radical anion of VK₁ in organic solvents. The unusualg tensor magnitude of A ₁ ^·? is explained by the hydrophobic binding pocket of this radical. The hyperfine couplings and the spin (and charge) density distribution is very different for A ₁ ^.? in PS I and VK ₁ ^·? in frozen alcoholic solution. This is attributed to a rather strong one-sided hydrogen bond to A ₁ ^·? . The presence of a hydrogen bond to A ₁ ^·? has only a minor effect ong. The hyperfine coupling constants of A ₁ ^·? determined from the radical pair spectra deviate only slightly from those derived from photoaccumulated A ₁ ^·? in PS I treated with dithionite at high pH. ENDOR resonances of the proton in a H bond were detected and an estimate of the strength and geometry of this bond to A ₁ ^·? was obtained. The significance of the hydrogen bond and other (hydrophobic) interactions of A₁ with the surrounding are briefly discussed.     

The decay of the Bethe-Salpeter kernel inP(ϕ)2 quantum field models

We extend methods of high temperature expansions to show that for even weakly coupledP(?)₂ quantum field models the Bethe-Salpeter kernel has 4 particle decay. More precisely ifK denotes the Euclidean Bethe-Salpeter kernel $$|K(x_1 ,x_2 ,x_3 ,x_4 )| \leqq Oe^{ - m_0 (1 - \varepsilon )d_2 } ,$$ wherex=(x ⁰,x ¹),d ₂=2|x ₁ ⁰ +x ₂ ⁰ ?x ₃ ⁰ ?x ₄ ⁰ |+|x ₁ ⁰ ?x ₂ ⁰ |+|x ₃ ⁰ ?x ₄ ⁰ | and ε(λ)→0 as λ→0. Our methods apply to otherr particle irreducible kernels.     

Potentiodynamic studies on corrosion of copper by chloride ions and its inhibition by inorganic and organic ions in aqueous buffer solution

Electrochemical oxidation of copper in aqueous phosphate buffer solution leads to the formation of passive films, which breakdown in the presence of aggressive chloride (Cl^?) ions. The addition of Cl^? ions in the medium causes shift in current and potential for both cathodic and anodic peaks. At low Cl^? ion concentrations, the corrosion current is greatly enhanced and continues to increase up to a certain concentration, after which it decreases. The effect of inorganic ions, chromate (CrO ₄ ^2? ) and tungstate (WO ₄ ^2? ), and organic ions, acetate (CH₃COO^?) and oxalate (C₂O ₄ ^2? ), on the formation and breakdown of passive films in aqueous buffer solution containing 0.10 M Cl^? ions have also been investigated. All of the ions inhibit corrosion of copper in the presence of aggressive Cl^? ions following the order of overall inhibition efficiency of CrO ₄ ^2? > C₂O ₄ ^2? > WO ₄ ^2? > CH₃COO^? under the experimental conditions.     

Cation distribution of the system Zn1−xCoxFeMnO4 by x-ray,electrical conductivity and Mössbauer studies

Structural, electrical and Mössbauer studies were carried out for the system Zn_1?xCo _x Fe MnO₄. It is observed that forx?0.6, the ionic configuration of the system is Zn _1?x ²⁺ Mn _x ²⁺ [Co _x ³⁺ Mn _1?x ³⁺ Fe³⁺]O ₄ ^2? and forx?0.8 Fe³⁺ ions occupy tetrahedral site also. On the basis of electrical and Mössbauer studies a probable valence distribution of CoMnFeO₄ has been suggested. All the compounds showed positive values of thermoelectric coefficient and electrical conduction takes place by a hopping mechanism. Activation energy and thermoelectric coefficient values decreased with decrease in concentration of Zn²⁺ ions. The compounds possess low mobility values varying between 10^?7 and 10^?9 cm²/V sec.     

Ionization and dissociative ionization of methane molecules

A technique for mass-spectrometric investigation of the yield of positive ions produced by direct and electron-impact dissociative ionization of methane molecules is described, and respective experimental data are presented. Doubly charged C ₂ ⁺ , CH ₃ ²⁺ , and CH ₄ ²⁺ ions, as well as singly charged D ₂ ⁺ , CD ₃ ⁺ , and CD ₄ ⁺ ions, are detected in the mass spectrum of a methane molecule at electron energy U _e = 90 eV for the first time. From ionization efficiency curves, the ionization energy of the parent molecule and the appearance energy of fragment ions are determined. The ionization energy of the CH₄ molecule is found to be 12.62 ± 0.20 eV. Electron-molecular reactions that may take place when a low-energy electron beam interacts with a methane molecule are analyzed. The ionization process and the formation of methane molecule fragments are studied.     

Leading/nonleading charm-production asymmetry in Σ− p interactions

The asymmetry between the spectra of leading and nonleading charmed mesons that was measured in Σ^? A interactions at p _L=340 GeV/c in the WA89 experiment is described within the Model of Quark-Gluon Strings (QGS model also known as QGSM) under the assumption that there is a fraction of charmed sea quark-antiquark pairs (intrinsic charm) in an interacting hyperon. It is shown that the asymmetries between D ^?-and D ⁺-meson spectra and between D _s ^? -and D _s ⁺ -meson spectra can be approximated by QGSM curves obtained with the same string-fragmentation parameter, a ₁=10, and the same intrinsic-charm fraction, $\delta _{c,\bar c} = 0.01$ , as those that were used in describing D _s ^? /D _s ⁺ -meson asymmetry of π^? A experiments in previous studies. The asymmetry between the spectra of Λ_c and $\bar \Lambda _c $ that was measured in Σ^? A collisions at p _L=600 GeV/c in the E781 experiment is also described within this scheme. The QGSM results are compared with the results of the calculations in the next-to-leading approximation of perturbative QCD that were performed by other authors.     

Production and loss of N 2 + , Ne+ and Ne 2 + during the decay period of plasmas produced in neon-nitrogen mixtures

Studies of the time dependencies of the number density of N ₂ ⁺ , Ne⁺ and Ne ₂ ⁺ ions have been made during the decay period of plasmas produced in neon containing various concentrations of nitrogen molecules. Reaction rate constants were obtained for N ₂ ⁺ +N₂+Ne→N ₄ ⁺ +Ne((1.2±0.2)×10^?29 cm⁶ sec^?1) and Ne⁺+N₂→N ₂ ⁺ + Ne ((2.9±0.3) × 10^?12 cm³ sec^?1). The ambipolar diffusion coefficient of N ₂ ⁺ in neon was found to beD _a p _o =350±20 cm² sec^?1 Torr.     

Optical and electrochemical properties of cyclometalated Pd(II) and Pt(II) complexes with a metal-metal chemical bond

Cyclometalated [M(C^N)(μ-(N-S))]₂ complexes ((M = Pd(II), Pt(II)), (C^N)^? are the deprotonated forms of 2-tolylpyridine and benzo[h]quinoline, and (N-S)^? are pyridine-2-thiolate and benzothiazole-2-thiolate ions) are studied by ¹H NMR, IR, electronic-absorption, and emission spectroscopy, as well as by voltammetry. It is shown that the formation of the metal-metal chemical bond and the σ _dz2 ^* orbital as a HOMO of complexes leads to the long-wavelength spin-allowed (410–512 nm) and spin-forbidden (595–673 nm) optical transitions σ _dz2 ^* ?π _(C^N) ^* in the absorption and phosphorescence spectra, as well as to the two-electron and successive one-electron oxidation with the formation of binuclear Pt(III) and Pd(III) complexes. The substitution of Pt(II) by Pd(II) is characterized by hypso- and bathochromic shifts of the spin-allowed and forbidden σ _dz2 ^* ?π _(C^N) ^* optical transitions in the absorption and phosphorescence spectra of complexes, by phosphorescence quenching of Pd(II) complexes in liquid solutions, and by an anodic shift of the oxidation potential of Pd(II) complexes compared with Pt(II) complexes.     

Investigation of N 2 + (C 2Σ u + → X 2Σ g + fluorescence excited through auger decay of the 1s −1π* resonance

A theoretical investigation of N ₂ ⁺ (C ²Σ _u ⁺ → X ²Σ _g ⁺ molecular fluorescence excited through the Auger decay of the 1s ^?1π* resonance is carried out. The fluorescence cross sections are calculated with due regard for the dependence of the matrix element of the C → X dipole transition on the internuclear distance, the interference between channels of excitation via different vibrational levels v _r of the 1s ^?1π* resonance, the rotational structure of the fluorescence band, and the predissociation of the N ₂ ⁺ C ²Σ _u ⁺ v′ ≥3) states. The calculated cross sections are in good agreement with the experimental results of recent measurements. The results of the calculations have demonstrated that the observed dependence of the cross section of the (C ²Σ _u ⁺ (v′) → X ²Σ _g ⁺ (v″) fluorescence on the excitation energy and the fluorescence wavelength for a group of bands with equal values of the difference Δv = v′ ? v″ is associated with transitions between the vibrational levels of the electronic states involved in the excitation and subsequent cascade decay of the 1s ^?1π* resonance: N₂ (v ₀ = 0) → N*₂(1s ^?1π*(v _r)) ? N ₂ ⁺ : (C ²Σ _u ⁺ (v′) → X ²Σ _g ⁺ (v″).     

Fragmentation processes of vanadium and niobium oxide clusters sputtered by ion bombardment

The mass distribution of emitted V _n O _m ^? and Nb _n O _m ^? clusters and their unimolecular decay by all stoichiometrically possible fragmentation channels, which takes place under the sputtering of niobium and vanadium surfaces and blowing by oxygen, are studied. It is shown that the formation, excitation, and unimolecular fragmentation of V _n O _m ^? and Nb _n O _m ^? clusters can be described by a statistical recombination mechanism. Clusters are formed over the target surfaces as a result of binary collisions of independently sputtered ions, atoms, and molecules.     

Near resonance charge transfer from a laser excited donor state

A laser induced charge transfer from Na(3p) to hydrogen-ions at different kinetic energies has been studied. An enhancement factor of about 90% in the production rate of Lyman-α radiation has been demonstrated to occur only with H⁺ and Na(3p) atoms reaction; no enhancement was observed with either H ₂ ⁺ or H ₃ ⁺ ions. Absolute cross-section for the production of Lyman-α radiation during the collision of H⁺, H ₂ ⁺ and H ₃ ⁺ ions and Na(3p) and Na(3s) atoms have been measured in the energy range 1–600eV. The charge exchange reactions involving hydrogen-ions and Na(3p) atoms created by two different methods have also been compared.     

Search for the K L 0 → π0ν \tilde v decay at the INEP U-70 accelerator: The KLOD project

The rare decay K _L ⁰ → π⁰ν $ \tilde v $ branching ratio measurement is one of the clearest Standard Model test. Calculations based on the SM predict Br(K _L ⁰ → π⁰ν $ \tilde v $ ) ≈ 2.8 × 10^?11, but the most accurate experimental value Br(K _L ⁰ → π⁰ν $ \tilde v $ ) < 6.7 × 10^?8 (90% C.L.). We present design of a new experimental setup KLOD (U-70 accelerator, IHEP, Protvino) for K _L ⁰ → π⁰ν $ \tilde v $ branching ratio measurement. Sensitivity of the KLOD experiment will be enough for registration of 2.4 events K _L ⁰ → π⁰ν $ \tilde v $ for every 10 days of the data taking (according to SM predictions).     

Studying track electrons in frozen aqueous solutions by means of emission Mössbauer spectroscopy

It is shown by means of emission Mössbauer spectroscopy that the reactivity of NO ₃ ^? cations with quasi-free track electrons exceeds those of H₃O⁺, ClO ₄ ^? , and HSO ₄ ^? ions by a factor of only three. This is in drastic contradiction to published assertions that these values differ by two orders of magnitude. An explanation for this discrepancy is proposed.     

Spin states of cobalt and the thermodynamics of Sm1 − x Ca x CoO3 − δ solid solutions

In the rare-earth SmCoO₃ perovskite, Co³⁺ ions at low temperatures appear to be in the low-spin state with S = 0, t _2g ² e _g ⁰ . If Ca²⁺ ions partially substitute Sm³⁺ ions, oxygen deficient Sm_{1 ? x} Ca _x CoO_{3 ? δ} solid solutions with δ = x/2 appear. The oxygen deficiency leads to the formation of pyramidally coordinated cobalt ions Co _pyr ³⁺ in addition to the existing cobalt ions Co _oct ³⁺ within the oxygen octahedra. Even at low temperatures, these ions have a magnetic state, either S = 1, t _2g ⁵ e _g ¹ or S = 2, t _2g ⁴ e _g ² . At low temperatures, the magnetization of Sm_{1 ? x} Ca _x CoO_{3 ? δ} is mainly determined by the response of Co _pyr ³⁺ ions. Owing to the characteristic features of the crystal structure of the oxygen deficient perovskite, these ions form a set of nearly isolated dimers. At high temperatures, the magnetization of Sm_{1 ? x} Ca _x CoO_{3 ? δ} is mainly determined by the response of Co _oct ³⁺ ions, which exhibit a tendency to undergo the transition from the S = 0, t _2g ⁶ e _g ⁰ state to the S = 1, t _2g ⁵ e _g ¹ or S = 2, tt _2g ⁴ e _g ² state. In addition, the magnetization and specific heat of the solid solutions under study include the contribution from the rare-earth subsystem, which undergoes a magnetic ordering at low temperatures.