Metastable helium cluster He<Stack><Subscript>4</Subscript><Superscript>*</Superscript></Stack>

The existence of a metastable cluster He ₄ ^* with total spin S = 2 is predicted. The cluster consists of two covalently bound excited spin-polarized triplet He ₂ ^* molecules and is rectangular in shape. The electron wavefunctions, the dependence of the energy He ₄ ^* system on the distance between the He ₂ ^* triplet molecules, the atomic spacing, the frequency spectrum of natural oscillations of the cluster, and other characteristics are calculated from first principles. It is shown that the metastable state is formed if one of the excited He ₂ ^* molecules is in the ³Σ _u ⁺ state, while the other is in the ³Π_g state. The radiation lifetime τ of the metastable cluster He ₄ ^* is calculated; it is found to range from 100 to 200 s, which is much longer than the lifetime τ ≈ 20 s of the triplet molecule He ₂ ^* (³Σ _u ⁺ ). The height U ≈ 0.5 eV of the potential barrier preventing the departure from the local energy minimum is determined. The energy E_acc ≈ 9 eV/atom accumulated in the He ₄ ^* cluster is calculated; this energy considerably exceeds the energy of known chemical energy carriers. It is shown that the accumulated energy is released virtually completely during decomposition of the He ₄ ^* cluster into individual helium atoms. This means that helium clusters are a promising material with a high accumulated energy density (HEDM).     

H<Subscript>3</Subscript>O<Stack><Subscript>2</Subscript><Superscript>-</Superscript></Stack> ions with a strong quasi-symmetrical H-bond and their hydration in aqueous solutions of NaOH and KOH

Ion-molecular interactions in aqueous solutions of NaOH (0–47.8%) and KOH (0–51.95%) are studied by multiple frustrated total internal reflection IR spectroscopy. Interpretation of the spectra and analysis of the spectral data are performed based on the results of DFT calculations (B3LYP/6-31++G(d, p)) of the characteristics of the free and double hydrated H₃O ₂ ^- ion. It is established that the changes in the IR spectra of NaOH and KOH aqueous solutions caused by increasing alkali concentration are due to the formation of H₃O ₂ ^- ions with a strong quasi-symmetrical hydrogen bond and their subsequent hydration by one or two water molecules. The influence of the cation nature on the degree of hydration of H₃O ₂ ^- ions is demonstrated. The equilibrium concentrations of monohydrate (H₃O ₂ ^- ? H₂O) and dihydrate (H₃O ₂ ^- ? 2H₂O) are calculated and their IR continuous absorption spectra are isolated.     

Manifestation of nonuniformity in the electron charge distribution in H<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> molecular ions colliding with each other

The anomalous character of threshold properties in the ion-molecule reactions H ₂ ⁺ + H ₂ ⁺ → H ₃ ⁺ + p and H ₂ ⁺ + H ₂ ⁺ → H + p + H + p has been theoretically analyzed. It has been shown that these reactions proceed through the formation of the intermediate H ₄ ⁺⁺ complex. Molecules H ₂ ⁺ in the collision process are described by a chemical model, where the positive charge is concentrated in one of the nuclei. The calculations of the reaction cross sections are in good agreement with the experimental data. It has been shown that the chemical model of the H ₂ ⁺ molecule can be consistently explained only in terms of dynamic interactions, i.e., polarization forces and van der Waals forces.     

Absolute cross-sections and kinetic-energy-release distributions for electron-impact ionization and dissociation of CD<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack>

Absolute cross-sections have been measured for electron-impact dissociativeexcitation and ionization of CD ₂ ⁺ leading toformation of CD ₂ ²⁺ , CD⁺, C⁺,D ₂ ⁺ and D⁺. The animated crossed-beams methodis applied in the energy range from the reaction threshold up to 2.5 keV.The maximum total cross-sections are found to be (1.2±0.1)×10^-17 cm², (6.1±0.7)×10^-17 cm², (6.4±0.7)×10^-17 cm², (26.3±3.8)×10^-19 cm² and (14.9±1.4)×10^-17 cm² forCD ₂ ²⁺ , CD⁺, C⁺,D ₂ ⁺ and D⁺ respectively. Individualcontributions for dissociative excitation and dissociative ionization aredetermined for each singly-charged product, which are of significantinterest in fusion plasma edge modelling and diagnostics. Conforming to thescheme recently applied in the CD ₄ ⁺ and in theCD ₃ ⁺ articles, the cross-sections are presented inclosed analytic forms convenient for implementation in plasma simulationcodes. Kinetic-energy-release distributions are determined for each ionicfragment at selected electron energies.     

Secondary ion emission from a GaAs single crystal upon bombardment with Bi<Stack> <Subscript> <Emphasis Type="Italic">m</Emphasis> </Subscript> <Superscript>+</Superscript> </Stack> cluster ions

Secondary-ion mass spectra and energy distributions upon bombarding a gallium arsenide single crystal using Bi_m⁺(m = 1–5) cluster ions with energies of 2–12 keV are investigated. The gallium cluster ion yield grew nonadditively with the number of atoms in the cluster projectiles. A quasi-thermal component found in the energy spectra of secondary Ga⁺ and Ga₂⁺ ions is indicative of the occurrence of the thermal spike mode upon cluster ion bombardment. The quasi-thermal component in the yield of atomic Ga⁺ ions upon bombardment with Bi₂⁺–Bi₅⁺–ions is 35–75%.     

High-frequency EPR of Cr<Superscript>2+</Superscript> ions in CdGa<Subscript>2</Subscript>S<Subscript>4</Subscript>

High-frequency broad-band (65–240 GHz) EPR is used to study impurity centers of bivalent chromium in a CdGa₂S₄ crystal. It is found that the EPR spectra correspond to tetragonal symmetry. The spin Hamiltonian H = βB · g · S + B ₂ ⁰ O ₂ ⁰ + B ₄ ⁰ O ₄ ⁰ + B ₄ ⁴ O ₄ ⁴ with the parameters B ₂ ⁰ =23659±2 MHz, B ₄ ⁰ =1.9±1 MHz, |B ₄ ⁴ |=54.2±2 MHz, g_‖=1.93±0.02, and g_⊥=1.99±0.02 is used to describe the observed spectra. It is concluded that chromium ions occupy one of the tetrahedrally coordinated cation positions.     

Luminescence of excitons and antisite defects in Lu<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce single crystals and single-crystal films

The luminescence of excitons and antisite defects (ADs) was investigated, as well as the specific features of the excitation energy transfer from excitons and ADs to the activator (Ce³⁺ ion) in phosphors based on Lu₃Al₅O₁₂:Ce (LuAG:Ce) single crystals and single-crystalline films, which are characterized by significantly different concentrations of ADs of the Lu _Al ³⁺ type and vacancy-type defects. The luminescence band with λ_max = 249 nm in LuAG:Ce single-crystal films is due to the luminescence of self-trapped excitons (STEs) at regular sites of the garnet lattice. The excited state of STEs is characterized by the presence of two radiative levels with significantly different transition probabilities, which is responsible for the presence of two excitation bands with λ_max = 160 and 167 nm and two components (fast and slow) in the decay kinetics of the STE luminescence. In LuAG:Ce single crystals, in contrast to single-crystal films, the radiative relaxation of STEs in the band with λ_max = 253.5 nm occurs predominantly near Lu _Al ³⁺ ADs. The intrinsic luminescence of LuAG:Ce single crystals at 300 K in the band with λ_max = 325 nm (τ = 540 ns), which is excited in the band with λ_max = 175 nm, is due to the radiative recombination of electrons with holes localized near Lu _Al ³⁺ ADs. In LuAG:Ce single crystals, the excitation of the luminescence of Ce³⁺ ions occurs to a large extent with the participation of ADs. As a result, slow components are present in the luminescence decay of Ce³⁺ ions in LuAG:Ce single crystals due to both the reabsorption of the UV AD luminescence in the 4f-5d absorption band of Ce³⁺ ions with λ_max = 340 nm and the intermediate localization of charge carriers at ADs and vacancy-type defects. In contrast to single crystals, in phosphors based on LuAG:Ce single-crystal films, the contribution of slow components to the luminescence of Ce³⁺ ions is significantly smaller due to a low concentration of these types of defects.     

Specific features of the three-electron <Emphasis Type="Italic">KL</Emphasis><Stack><Subscript>2, 3</Subscript><Superscript>2</Superscript></Stack> ionization of silicon atoms upon near-threshold photoabsorption

The shape and relative intensity of the group of the Kα_5–8 satellites (radiative transitions KL _{2, 3} ² )-L _{2, 3} ³ of Si atoms are experimentally studied upon photoabsorption near and far from the KL _{2, 3} ² ionization threshold. The satellites were excited near the ionization threshold by lines of the characteristic L spectrum and bremsstrahlung radiation from Nb and Mo anodes and far from the threshold by the L spectrum and bremsstrahlung radiation from an Ag anode and by monochromatized Kα_{1, 2} radiation from a Ti anode. It is established that the probability P(L _{2, 3} ² ) of formation of two additional 2p vacancies during KL _{2, 3} ² photoabsorption of Si atoms near the energy threshold is by a factor of 1.5 lower than that during photoionization in a more distant energy region beyond the threshold. At the same time, the P(L _{2, 3} ² )/P(L _{2, 3}) ratio remains invariable for the absorbed photons throughout the energy range studied. It is demonstrated that, as the KL _{2, 3} ² ionization threshold is approached, an intensity redistribution occurs among the components of the group of the Kα_5–8 lines, which reflects a decrease in the excitation cross section ratio σ(⁴ P)/σ(² P) of the ⁴ P and ² P terms of the KL _{2, 3} ² configuration. A conclusion is drawn that the effects of suppression of the generation of P terms of higher multiplicity during the KL _{2, 3} and KL _{2, 3} ² near-threshold photoionizations are of a common nature.     

Exotic molecular states in a strong magnetic field: H<Stack><Subscript>3</Subscript><Superscript>(2+)</Superscript></Stack> ion

The existence of the molecular ion H ₃ ⁽²⁺⁾ in a magnetic field in a triangular and a linear configuration is discussed. A variational method (with an optimization of the form of the vector potential) is used. It is shown that, in the range of magnetic fields 10⁸<B<10¹¹ G, the system (pppe), with the protons forming an equilateral triangle perpendicular to the magnetic line, has a well-pronounced minimum in the total energy. Also, for B?10¹⁰ G, if the protons are situated along a magnetic line (linear configuration), a well-pronounced minimum in the total energy appears. Both configurations are unstable under the decays H(atom) + p + p and H ₂ ⁽⁺⁾ + p. A possible connection between the H ₃ ⁽²⁺⁾ molecular ion and a recently discovered absorption feature in a neutron-star atmosphere is discussed.     

Optical characteristics of radiation from N<Stack><Subscript>2</Subscript><Superscript>*</Superscript></Stack> dimers in a barrier discharge

The spectral and power characteristics of radiation of the second positive system of nitrogen (C ³Π _u → B ³Π _g ) in Ar-N₂ and Ar-N₂-Cl₂ mixtures excited by barrier discharge have been studied experimentally. Addition of argon to N₂ increased the radiation power by sixfold. In the triple mixture Ar-N₂-Cl₂ = 210/0.5/0.005, minor chlorine additions increased the intensity of the C ³Π _u → _B ³Π _g transition by 26% compared to Ar-N₂ mixtures. Radiation power density of 2.7 mW/cm² has been achieved. In both binary and triple mixtures, the second positive system of nitrogen was the major contributor to radiation, while the contributions of the fourth positive system of N ₂ ^* (D ³Σ _u ⁺ → B ³Π _g ), the Vegard-Kaplan transition of N ₂ ^* (A ³Σ _u ⁺ → X ¹Σ _g ⁺ ), and the D′ → A′ band of Cl ₂ ^* were negligibly small.     

On double magicity of the <Stack><Subscript>28</Subscript><Superscript>68</Superscript></Stack>Ni<Subscript>40</Subscript> nucleus

Single-particle energies E _nlj of neutron states in the ₂₈ ⁶⁸ Ni₄₀ nucleus are estimated on the basis of extrapolation of the experimental values of E _nlj in the ^58,60,62,64Ni isotopes. The data obtained are compared with the results of calculation within the dispersion optical model.     

Study of the formation and unimolecular fragmentation of Si<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>O<Stack><Subscript><Emphasis Type="Italic">m</Emphasis></Subscript><Superscript>+</Superscript></Stack> clusters under ion bombardment

The dependences of the emission and fragmentation of clusters sputtered by Xe⁺ ions from the surface of Si _n O _m ⁺ on the oxygen pressure near the bombarded surface are studied using secondary ion mass spectrometry. It is shown that the process of Si _n O _m ⁺ cluster formation under ion bombardment can be described within the framework of the mechanism of combinatorial synthesis by taking into account the mutual reversibility of the reactions of formation and unimolecular decay.     

Geometry of the internal dynamics of C<Subscript>2</Subscript>H<Stack><Subscript>3</Subscript><Superscript>+</Superscript></Stack> carbocation

Using the symmetry group chain methods, the internal dynamics of the simplest carbocation, C₂H ₃ ⁺ , is analyzed under the traditional assumptions that the equilibrium structures of the carbocation are planar and that the nonrigid motion between them is in-plane. This geometry of the internal dynamics is shown to agree with the data of the microwave spectroscopy on the splittings of rotational energy levels caused by the nonrigid motion. Previously, this statement was based on the model that violated the requirement of self-adjointness of operators of physical quantities.     

Synthesis and electrical properties of new perovskite-like <Emphasis Type="Italic">A</Emphasis>Mn<Subscript>3</Subscript>V<Subscript>4</Subscript>O<Subscript>12</Subscript> (A = Ca,Ce, and Sm) compounds

AMn₃V₄O₁₂ (A = Ca, Ce, and Sm) compounds with a perovskite structure are synthesized at high pressures and temperatures. The crystalline structure of these compounds (space group \(Im\bar 3\)Z = 2) is determined via X-ray analysis. If ions in the A sublattice are changed in the order Ca²⁺–Sm³⁺–Ce³⁺, the valence is redistributed from Ca²⁺Mn₃²⁺V₄⁴⁺O₁₂ to Sm³⁺Mn₃²⁺V₄^3.75+O₁₂, and to Ce³⁺Mn₃²⁺V₄^3.75+O₁₂. The temperature dependences of the electrical resistivity are studied.     

Spectroscopic study of erbium-activated crystals of double calcium yttrium fluoride Ca<Subscript>0.89</Subscript>Y<Subscript>0.11</Subscript>F<Subscript>2.11</Subscript>:Er<Superscript>3+</Superscript>: I. Intensity of spectra and luminescence kinetics

Ca_0.89Y_0.11F_2.11:Er³⁺ (CYF:Er) crystals with an erbium content of 1–15 at % have been grown. The optical spectra and luminescence kinetics of CYF:Er crystals have been investigated at low (～5 K) and room temperatures. Based on an analysis of the absorption spectra at low temperature, the structure of Stark splitting of erbium levels in CYF:Er crystals is determined. Room-temperature absorption spectra are used to calculate the spectra of absorption cross sections and oscillator strengths of transitions from the erbium ground state to excited multiplets. It is shown that the absorption spectrum of CYF:Er crystals contains broad bands in the ranges of 790–815 and 965–980 nm, which correspond to the range of emission of laser diodes. For the band peaking near 967 nm, the peak absorption cross section is σ _abs ^max = 2.7 × 10^?21 cm². The intensity parameters are determined by the Judd-Ofelt method to be Ω₂ = 1.39 × 10^?20, Ω₄ = 1.34 × 10^?20, and Ω₆ = 2.24 × 10^?20 cm². The radiative transition probabilities, radiative lifetimes, and branching ratios are calculated with these values. The luminescence decay kinetics from excited erbium levels upon selective excitation is investigated and the experimental lifetimes of the 4F _9/2, ⁴ S _3/2, and ⁴ G _11/2 radiative erbium levels are determined. The dependences of multiphonon relaxation rates on the energy gap in CYF:Er crystals are obtained. The rates of nonradiative multiphonon relaxation from radiative erbium levels are determined.     

Critical behavior of La<Subscript>0.825</Subscript>Sr<Subscript>0.175</Subscript>MnO<Subscript>2.912</Subscript> anion-deficient manganite in the magnetic phase transition region

For La _0.825 ³⁺ Sr _0.175 ² +Mn³⁺O _2.912 ^2? anion-deficient manganite, the specific magnetization, the dynamic magnetic susceptibility, and the heat capacity are investigated. This material is found to be an inhomogeneous ferromagnet below the Curie point T _C ≈ 122 K, which is much lower than the Curie point determined for the stoichiometric composition (T _C ≈ 268 K). An increase in magnetic field by two orders of magnitude leads to an increase in the Curie temperature by ΔT ≈ 12 K. The presence of oxygen vacancies leads to the frustration of a part, namely, V _fr ≈ 22%, of the indirect Mn³⁺-O-Mn³⁺ exchange interactions, but the spin glass state is not realized. The ferromagnetic matrix of the material under study is characterized by a scatter in the exchange interaction intensities. The heat capacity is found to exhibit an anomalous behavior. Based on the Banerjee magnetic criterion, it is established that the ferromagnet-paramagnet transition observed for La _0.825 ³⁺ Sr _0.175 ²⁺ Mn³⁺O _2.912 ^2? anion-deficient manganite is a second-order thermodynamic phase transition. The mechanism and origin of the critical behavior of the system under investigation are discussed.     

Investigation of low-lying levels of the <Stack><Subscript>4</Subscript><Superscript>8</Superscript></Stack>Be nucleus in the multiquantum approximation of the orthogonal scheme

In the multiquantum approximation of the orthogonal scheme, specific calculations for the energies and radii of the ₄ ⁸ Be nucleus are performed with allowance for all states characterized by the λ=[44] Young diagram, the quantum numbers K_min and K_min+2 of the O(3(A?1)) group, and the quantum numbers E=K+2N (N≤9) of the U(3(A?1)) group. The convergence of the results with respect to the extension of the basis is studied, and the structure of relevant wave functions is revealed. The results of these calculations are compared with the results obtained in the analogous approximation of the unitary scheme.     

Electronic excitations and defects in nanostructural Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

A time-resolved cathodo-and photoluminescence study of nanostructural modifications of Al₂O₃ (powders and ceramics) excited by heavy-current electron beams, as well as by pulsed synchrotron radiation, is reported. It was found that Al₂O₃ nanopowders probed before and after Fe⁺ ion irradiation have the same phase composition (the γ-phase/δ-phase ratio is equal to 1), an average grain size equal to ～17 nm, and practically the same set of broad cathodoluminescence (CL) bands peaking at 2.4, 3.2, and 3.8 eV. It was established that Al₂O₃ nanopowders exhibit fast photoluminescence (PL) (a band at 3.2 eV), whose decay kinetics is described by two exponential stages (τ₁ = 0.5 ns, τ₂ = 5.5 ns). Three bands, at 5.24, 6.13, and 7.44 eV, were isolated in the excitation spectrum of the fast PL. Two alternate models of PL centers were considered, according to which the 3.2-eV luminescence either originates from radiative relaxation of the P^? centers (anion-cation vacancy pairs) or is due to the formation of surface analogs of the F⁺ center (F _S ⁺ -type centers). In addition to the fast luminescence, nano-Al₂O₃ was found to produce slow luminescence in the form of a broad band peaking at 3.5 eV. The excitation spectrum of the 3.5-eV luminescence obtained at T = 13 K exhibits two doublet bands with maxima at 7.8 and 8.3 eV. An analysis of the luminescent properties of nanostructural and single-crystal Al₂O₃ suggests that the slow luminescence of nanopowders at 3.5 eV is due to radiative annihilation of excitons localized near structural defects.     

Average decay rate constants and excitation energies for metal clusters sputtered by SF<Stack> <Subscript>5</Subscript> <Superscript>+</Superscript> </Stack> and inert gas ions

Results from a comparative SIMS study of the fragmentation of metal clusters sputtered with atomic Xe⁺ and molecular SF₅⁺ ions are presented. It is shown that the average decay rate constants and, hence, the excitation energies of clusters of the same stoichiometry do not depend on the type of bombarding ions.     

Thermal quenching of luminescence of BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystals activated with Er<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> ions

Thermal quenching of interconfigurational 5d-4f luminescence of Er³⁺ and Tm³⁺ ions in BaY₂F₈ crystals is studied in the temperature range of 330–790 K. The quenching temperatures are ~575 and ~550 K for Er³⁺ and Tm³⁺, respectively. It is shown that quenching of 5d-4f luminescence of Tm³⁺ ions is caused by thermally stimulated ionization of 5d electrons to the conduction band.