Description of the torsional motion in the isotopically asymmetric ionic complexes ArH<Subscript>2</Subscript>D<Superscript>+</Superscript> and ArD<Subscript>2</Subscript>H<Superscript>+</Superscript>

The internal dynamics of the isotopically asymmetric ionic complexes ArH₂D⁺ and ArD₂H⁺ is considered to be a distorted dynamics of the isotopically symmetric ArH₃⁺ complex. By using the group chain methods, a rigorous algebraic model is constructed to describe the spectrum of the asymmetric complexes with an allowance for the torsional motion of the structure of hydrogen nuclei. The model is based on the geometrical group of symmetry of internal dynamics of the isotopically symmetric ionic complex, which is used here as a noninvariant group.     

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.     

Resonator effects of Ar<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> ionic excimer pumped by electron beam

The third continuum of argon from 200 to 270 nm is obtained by electron beam pumping argon. With the front mirror and the rear mirror, the resonator effects are observed at 240 and 220 nm. Compared with the intensity of fluorescence, the intensity near 240 nm increases more than 10 times when the resonator is formed. In order to explain the origin of the continuum, the kinetic model on Ar₂⁺ and Ar₂²⁺ ionic excimers pumped by electron beam is built and calculated. Based on the theoretical results, the Ar₂⁺ ionic excimer should be responsible for the continuum around 240 nm.     

Kinetics of Rb<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> and Rb<Superscript>+</Superscript> formation in laser-excited rubidium vapor

We have studied the formation of the molecular ion Rb₂⁺ and the atomic ion Rb⁺. These are created in laser excited rubidium vapor at the first resonance, 5s–5p and 5p-nl transitions. A theoretical model is applied to this interaction to explain the time evolution and the laser-power dependence of the population density of Rb⁺ and Rb₂⁺. A set of rate equations which describe: the temporal variation of the population density of the excited states; the atomic ion density; and the electron density, were solved numerically under the experimental conditions of Barbier and Cheret. In their experiment the Rb concentration was 1×10¹³cm⁻³ and the laser power was taken to be 50–500 mW at vapor temperature = 450 K. The results showed that the main processes for producing Rb₂⁺ are associative ionization and Hornbeck-Molnar ionization. The calculations have also showed that, the atomic ions Rb⁺ are formed through the Penning Ionization (PI) and photoionization processes. Moreover, a reasonable agreement between the experimental results and our calculations for the ion currents of the Rb⁺ and Rb₂⁺ is obtained.      

I. Electron-impact ionization and dissociation of C<Subscript>2</Subscript>H<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> and C<Subscript>2</Subscript>D<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack>

Absolute cross-sections for electron-impact ionization and dissociation of C₂H₂⁺ and C₂D₂⁺ have been measured for electron energies ranging from the corresponding thresholds up to 2.5 keV. The animated crossed beams experiment has been used. Light as well as heavy fragment ions that are produced from the ionization and the dissociation of the target have been detected for the first time. The maximum of the cross-section for single ionization is found to be (5.56 ± 0.03)× 10^-17 cm² around 140 eV. Cross-sections for dissociation of C₂ H₂⁺ (C₂D₂⁺) to ionic products are seen to decrease for two orders of magnitude, from C₂D⁺ (12.6 ± 0.3) × 10^-17 cm² over CH⁺(9.55 ± 0.06) × 10^-17 cm², C⁺ (6.66 ± 0.05) × 10^-17 cm², C₂⁺ (5.36 ± 0.27) × 10^-17 cm², H⁺ (4.73 ± 0.29) × 10^-17 cm² and CH₂⁺ (4.56 ± 0.27) × 10^-18 cm² to H₂⁺ (5.68 ± 0.49) × 10^-19 cm². Absolute cross-sections and threshold energies have been compared with the scarce data available in the literature.     

Absolute cross-sections and kinetic-energy-release distributions for electron-impact ionization and dissociation of CD<Stack><Subscript>3</Subscript><Superscript>+</Superscript></Stack>

Absolute cross-sections have been measured for electron-impact dissociative excitation and ionization of CD₂⁺ leading to formation of CD₂²⁺, CD⁺, C⁺, D₂⁺ and D⁺. The animated crossed-beams method is 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 for CD₂²⁺, CD⁺, C⁺, D₂⁺ and D⁺ respectively. Individual contributions for dissociative excitation and dissociative ionization are determined for each singly-charged product, which are of significant interest in fusion plasma edge modelling and diagnostics. Conforming to the scheme recently applied in the CD₄⁺ and in the CD₃⁺ articles, the cross-sections are presented in closed analytic forms convenient for implementation in plasma simulation codes. Kinetic-energy-release distributions are determined for each ionic fragment at selected electron energies.     

II. Electron-impact dissociative excitation of C<Subscript>2</Subscript>H<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> and C<Subscript>2</Subscript>D<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack>

Absolute cross-sections for electron-impact dissociative ionization of C₂ H₂⁺ and C₂ D₂⁺ to CH⁺, C⁺, C₂⁺ , H⁺, CH₂⁺ and C₂D⁺ fragments are determined for electron energies ranging from the corresponding threshold to 2.5 keV. Results obtained in a crossed beams experiment are analyzed to estimate the contribution of dissociative ionization to each fragment formation. The dissociative ionization cross sections are seen to decrease for more than an order of magnitude, from CH⁺ (5.37±0.10) × 10^-17 cm² over C⁺ (4.19± 0.16) × 10^-17 cm², C₂D⁺ (3.94±0.38) × 10^-17 cm², C₂⁺ (3.82±0.15) × 10^-17 cm² and H⁺ (3.37±0.21) × 10^-17 cm² to CH₂⁺ (2.66±0.14) × 10^-18 cm². Kinetic energy release distributions of fragment ions are also determined from the analysis of the product velocity distribution. Cross section values, threshold energies and kinetic energies are compared with the data available from the literature. Conforming to the scheme used in the study of the dissociative excitation of C₂H₂⁺ ( C₂ D₂⁺ )\left( {\rm C}_2 {\rm D}_2^+ \right), the cross-sections are presented in a format suitable for their implementation in plasma simulation codes.     

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.     

Modification of GaAs by medium-energy N<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> ions

The modification of GaAs with a 2500-eV beam containing N ₂ ⁺ and Ar⁺ ions is examined with Auger electron spectroscopy. Most implanted nitrogen atoms are found to react with the matrix, substituting arsenic atoms to produce a several-nanometer-thick layer of the single-phase GaAs_1−x N_x (x=6%) solid solution. The GaN phase is absent. Displaced arsenic atoms and nitrogen atoms unreacted with the matrix are present in the layer and on its surface. The former segregate, whereas the latter form molecules.     

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.     

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).     

Polymerization of solid C<Subscript>60</Subscript> under C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack> cluster ion bombardment

The structure transformation occurring in fullerene film under bombardment by 50 keV C₆₀⁺ cluster ions is reported. The Raman spectra of the irradiated C₆₀ films reveal a new peak rising at 1458 cm⁻¹ with an increase in the ion fluence. This feature of the Raman spectra suggests linear polymerization of solid C₆₀ induced by the cluster ion impacts. The aligned C₆₀ polymeric chains composing about 5–10 fullerene molecules have been distinguished on the film surface after the high-fluence irradiation using atomic force microscopy (AFM). The surface profiling analysis of the irradiated films has revealed pronounced sputtering during the treatment. The obtained results indicate that the C₆₀ polymerization occurs in a deep layer situated more than 40 nm below the film surface. The deep location of the C₆₀ polymeric phase indirectly confirms the dominant role of shock waves in the detected C₆₀ phase transformation.     

Frequency measurements in the b <Superscript>3</Superscript>Π(0<Subscript>u</Subscript><Superscript>+</Superscript>) - X <Superscript>1</Superscript>Σ<Subscript>g</Subscript><Superscript>+</Superscript> system of K<Subscript>2</Subscript>

Absolute transition frequencies of the b ³Π(0_u ⁺) - X ¹Σ_g ⁺ system of K₂ were measured in a molecular beam with Lamb dip absorption spectroscopy applying a frequency comb from a femtosecond pulsed laser. Both, K atoms and K₂ molecules are present in the beam and are expected to interact by collisions. The atoms can be deflected optically out of the beam, and thus the collision rate between K atoms and K₂ molecules is changed by about an order of magnitude. The molecular transition frequencies for low collisional rate are compared with those for high one. Limits for the collisional frequency shift within the beam are determined.     

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.     

Molecular dynamics study of the reaction C<Subscript>3</Subscript> + H <Subscript>3</Subscript><Superscript>+</Superscript>

Both a quantum molecular dynamic method and high level ab initio calculations (MP2, CCSD(T)) have been used to investigate the mechanism of the C₃ + H₃⁺ reaction, which is part of the ion chemistry in interstellar clouds. Furthermore statistic initial orientations in collision simulations have been set up in order to determinate reaction cross-sections and rate coefficients of all occurring reaction channels. Our analysis shows that the revealed mechanism is strongly determined by dynamic effects.     

Charge transfer in the collision system He<Superscript>2+</Superscript> + C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack>: Theory and experiment

Fullerenes are a direct link between atoms with discrete electronic energy levels and solids with a band structure and a well-defined surface. In this paper, we report on a quantum mechanical treatment of charge transfer and ionization in the ion-ion collision system ³He²⁺ + C ₆₀ ⁺ . This approach considers under- and over-barrier transitions through the one-dimensional barrier between the collision partners. The calculated cross sections for charge transfer compare favorably with experimental data measured in the center-of-mass energy range from 27 to 196 keV employing the crossed beams technique.     

Luminescence of Tl<Superscript>+</Superscript> ions in a KZnF<Subscript>3</Subscript> crystal

The luminescence spectra of a KZnF₃: Tl⁺ crystal are investigated in the energy range from 4.75 to 5.9 eV at temperatures of 10–300 K upon excitation into the A absorption band (5.7–6.3 eV). At T=300 K, the luminescence spectra exhibit an intense band with a maximum at 5.45 eV, which is attributed to single Tl⁺ ions substituted for K⁺ ions. The 5.723-eV intense narrow band observed at T<20 K is assigned to the ³Γ_1u-¹Γ_1g zero-phonon transition, which is weakly allowed by the hyperfine interaction. The luminescence decay is studied as a function of temperature. The main characteristics of the luminescence spectra are adequately described in terms of the semiclassical theory based on the Franck-Condon principle and the Jahn-Teller effect for an excited sp configuration of the Tl⁺ ion with the use of the parameters obtained earlier from analyzing the absorption spectra of the system under investigation.     

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.