Electron loss and capture to continuum from He and Ne atoms bombarded with He+-Ions

We have measured the cusp electron yield in coincidence with the transmitted charge state (He⁰, He⁺ and He⁺⁺) when³He⁺ collides with He and Ne under single collision conditions. For the first time this enables the electron capture to the continuum (ECC) yield to be directly compared with that from electron loss to continuum (ELC). While the ECC contribution is smaller than that from ELC at high projectile velocities (V _p >3 au) the data suggest that ECC will dominate belowV _p =2.8 au. The relevance of the results to the projectile velocity dependence of existing capture theories is discussed.     

Intra- and inter-atomic auger processes in collisions of low energy He++, He+, He* (23,S, 21 S) and Li+ with Li covered W(110) surfaces

Electron spectra from He⁺⁺, He⁺ and Li⁺ (10 to 1500 eV) ions colliding under grazing incidence with Li covered W (110) surfaces are reported. The results are compared with those obtained from thermal collisions of (2³ S; 2¹ S) metastable He atoms. In these collisions 1s vacancies are either produced during the collision event (energetic He⁺ (Li ⁺) collisions) or are brought into the collision (slow He⁺⁺ (He⁺, He*) collisions). Population of the 2s orbitals by two electrons produces states which decay by intraatomic Auger processes: we observe autoionization of He** (2s ²) and Li** (1s 2s ²) as well as autodetachment of He^?* (1s 2s ²). Alternatively the 1s-holes in the projectile or target (Li) can be filled by Auger processes involving one or two surface electrons. The processes leading to electron emission are studied as a function of the Li coverage in the submonolayer region (0≦Θ_Li≦1Ml) and as a function of the projectile energy. It is concluded that with one or two 1s vacancies present in the projectile the double capture of two surface electrons constitutes an important process responsible for electron emission of low work function surfaces.     

Thermal energy collisions between metastable Ne⋆(2p 53s,3 P 0, 2) and H2(X,1Σ g + )

A crossed beam experiment is used to investigate the Ne*(2p ⁵ 3s,³ P _{0, 2}) ? H₂(¹Σ _g ⁺ ) collision at thermal energy (67 meV). The H₂ beam is supersonic, the Ne* beam is thermal. Different collision processes have been analyzed separately by means of a double chopping technique combined with a time of flight measurement. Ions produced by Penning effect and chemi-ionization have been separated from scattered metastable atoms by an accelerating electric field small enough to preserve a reasonable angular resolution: δ?(ions)=±5.5°, δ?(Ne*)=±1°, which allows a determination of differential cross sections. The attenuation method, combined with an absolute measurement of the total H₂ flux, has been used to measure the total cross section: σ _t =940±220a ₀ ² . Differential cross sections have been obtained, in arbitrary but unique unit, for the following processes: (1) elastic collisions, for a mixture (1:3) of para- and ortho-hydrogen; (2) rotationally inelastic collisions:J=0→2; (3) Penning ionization resulting into H ₂ ⁺ ions; (4) chemiionization yielding NeH⁺ ions.     

Interpretation of collision induced dissociative charge-transfer processes in rare-gas molecule ions

We propose an interpretation of experimental measurements of dissociative charge-transfer processes X₂⁺+Y→X+X+Y⁺ (X=rare-gas atom) in terms of avoided-crossings of adiabatic potential surfaces. Model potential energy surfaces for a typical system (X=He, Y=Ne) are computed by the method of diatomics-in-molecules (DIM). The qualitative shapes of the surfaces suggest dynamical simplifications which can be embodied in a classical-mechanical trajectory model with “surface-hopping”. Analogy with earlier surface-hopping trajectory calculations and with trajectories for endothermic ion-molecule reactons provides a basis for understanding some of the major experimental findings for the He₂⁺-Ne reaction. The model viewpoint is also able to rationalize the observance (or non-observance) of other rare-gas reactions and can be extended to the case where Y=N₂, X=He.     

Scattering of low energy He2+ ions by Ne,Ar, and Kr atoms

Experimental studies of collisions of He²⁺ ions with Ne, Ar, and Kr atoms have been carried out at laboratory kinetic energies in the range 8 ? E₁ ? 10 eV. For each collision pair, relative differential cross sections for elastic scattering, and for the formation of He⁺ by single charge transfer [e.g., He²⁺ + R = He⁺ + (R⁺)^*] were measured. Information concerning the initial states of the charge transfer products was also obtained, from measurements of the kinetic energy distributions of the He⁺ + He = Ne⁺(2s 2p⁶²S) ± He⁺(²S), whereas for the other systems, transfer proceeds via a number of channels. The He⁺-ion kinetic energy measurements indicated that for He²⁺. Ar both Ar⁺ both Ar⁺ and Ar²⁺ are formed in transfer, and that for He²⁺, Kr only Kr²⁺ (and no Kr⁺) was formed.The differential elastic scattering patterns were analyzed by means of cross section calculations based on an approximate form of the optical model. These calculations indicated that the pronounced shoulders observed in the σ_el(θ) versus θ curves arose from scattering from an attractive potential well, in the presence of concurrent inelastic scattering. Using parametrized Morse potentials to represent the ground electronic states of (HeNe)²⁺, (HeAr)²⁺, and (HeKr)²⁺, the corresponding well-depth are estimated to be, respectively: 1.0 eV, 2.1 eV and 2.6 eV.     

Crossed beam study of He+-O2 charge transfer reactions in the collision energy range 0.5–200 eV

Energy spectra and angular distributions of the O⁺ and O ₂ ⁺ product ions resulting from the He⁺-O₂ charge transfer reaction have been measured in the collision energy range 0.5–200 eV using the crossed-beam method. The O ₂ ⁺ ions represent only a minor fraction of the reaction products (0.2–0.6% over the energy range measured). In the dissociative charge transfer reaction, four main processes are identified leading to O+O⁺ reaction products in different electronic states. Two different mechanisms can be distinguished, each being responsible for two of the observed processes:(i) a long-distance energy-resonant charge transfer process involving thec ⁴∑ _u ^? (v′=0) state of O ₂ ⁺ and(ii) a slightly exothermic charge transfer process via the (III)²∏ _u state of O ₂ ⁺ (with the exothermicity depending on the collision energy). Angle-integrated branching ratios and partial cross sections (in absolute units) have been determined. The branching ratios of the individual processes show a pronounced dependence on the collision energy. At low energies, the O⁺ product ions are preferentially formed in the² P ⁰ and² D ⁰ excited states. The angular distributions of the O⁺ product ions show an anisotropic behaviour indicating an orientation-dependent charge transfer probability in the He⁺ ?O₂ reaction.     

Polarisation effects in electron transfer reactions with laser excited Na(3P) at medium energies

We report new experimental data for the investigation of the role of electronic orbital alignment and orientation in charge transfer processes, in the medium energy range where the collision velocityv _c and the velocity of the active electronv _e are of the same order of magnitude. The results obtained for the H ₂ ⁺ -Na(3p) and He⁺-Na(3p) collisions are discussed in comparison with the experimental and theoretical findings obtained for the H⁺-Na(3p) system. Recent time-of-flight measurements for charge transfer in Li⁺-Na(3s and 3p) collisions are also presented.     

The unimolecular decomposition of chemically activated complexes: Cross sections for the chemi-ionization of Ca,Sr, Ba with NF3 and SF6

Integral reactive cross sections for chemi-ionization have been measured in a crossed-beam experiment for Ba, Sr + SF₆ → BaF⁺, SrF⁺ + SF₅^? and Ca, Sr + NF₃ → CaF⁺, SrF⁺ + NF₂^? at collision energies E_c.m. < 4 eV. The experimental results confirm a collision complex. The applicability of RRKM theory to chemi-ionization of polyatomic molecules is discussed. The presence of competing neutral-product reactions, included in the calculation, is important for the determination of dynamical and statistical properties of the intermediate states formed. The slope of the chemi-ionization cross section as a function of collision energy indicates directly that all vibrational degrees of freedom are activated.     

He++N2 Charge Transfer Reaction: An Ab initio Analysis

An ab initio analysis on the involved potential energy surfaces is presented for the investigation of the charge transfer mechanism for the He⁺+N₂ system. At high collision energy, as many as seven low-lying electronic states are observed to be involved in the charge transfer mechanism. Potential energy surfaces for these low-lying electronic states have been computed in the Jacobi scattering coordinates, applying multireference configuration interaction level of theory and aug-cc-pVQZ basis sets. Asymptotes for the ground and various excited states are assigned to mark the entrance (He⁺+N₂) and charge transfer channels (He+N₂⁺). Nonadiabatic coupling matrix elements and quasi-diabatic potential energy surfaces have been computed for all seven states to rationalize the available experimental data on the charge transfer processes and to facilitate dynamics studies.     

Integral cross sections for ion—molecule reactions. I. The guided beam technique

A technique is described, that allows the measurement of integral cross sections for ion-molecule reactions and electron-transfer processes in the energy range from typically 0.1 to 20 eV (lab). Basically similar to the tandem mass spectrometer method, it uses inhomogeneous oscillatory electric fields for the storage and guidance of the primary ions and for the collection of the secondary ions. By these means a reduction of the number of excited ions in the primary beam and a good definition of the kinetic energy are obtained, together with a collection and detection probability for the secondary ions, that approaches unity for all scattering angles in a broad energy band. Tire ion beam intensity (10⁵ to 10⁷ ions per second) is only weakly dependent on the kinetic energy down to typically 0.15 eV (lab). The distribution of the collision energies is mainly determined by the thermal motion of the reactant gas in the scattering chamber (T ≈ 300 K). Measurements are reported for the reactions Ar⁺ + D₂ → ArD⁺ + D and Ne⁺ + CO → C⁺ Ne+O.     

Polarization studies of Lyman-α radiation emitted in atom-H2-molecule collisions

A polarization study of Lyman-α radiation emitted in collisions of H⁺, H, He⁺, and He projectiles with H₂ molecules has been performed at projectile energies ranging from 1–25 keV. In H⁺?H₂ and H?H₂ collisions, the measured linear polarization is negative at low incident velocities, indicating a preferred alignment of the excited electron charge cloud perpendicular to the incident projectile direction. This is taken as significance for a rotational coupling which in these two collision systems predominantly populates the H(2p _±1) substates. In He⁺?H₂ and He?H₂ collisions, the measured linear polarization is about zero and independent of the projectile energy. In these more asymmetric systems,a′?a′ and a′?a″ couplings are now of comparable magnitude.     

Luminescence in near-thermal charge exchange. II. He+ + H2O and He+ + D2O

An ICR spectrometer fitted with synchronous photon counting equipment is used to study the emission produced by near-thermal (? 0.1 eV) collisions between He⁺ and H₂O (D₂). Within the investigated wavelength region, 185 to 500 nm, the only significant emission features are the A³Π (υ' ? 3) → X³Σ^? bands in OH⁺ and OD⁺, and the A²Σ⁺ → X²Π(0.0) band in OH and, possibly, in OD. The corresponding excitation rate constants represent only ? 2% of the total He⁺/H₂O (D₂O) charge transfer. The resonant electron-jump model for thermal-energy charge exchange is discussed in the light of recent information on the He⁺/H₂O reaction and on the excited states of H₂O⁺ and their excitation by electron and photon impact on H₂O (D₂O).     

A new method for the measurement of vibrational-state-selected ion-molecule reactions at thermal energies

A photoelectron-secondary-ion-coincidence method is described that allows us to determine the relative vibrational-energy-dependent cross sections for reactions of molecular ions with neutral atoms or molecules at thermal energies. Results for reactions of H₂⁺(ν) in vibrational states ν = 0–8 with H₂(H₃⁺), Ne(NeH⁺) and He(He⁺) are reported.     

Ab initio study of small He cluster ions He n + ,n=2, 3, 4, 5, and low-lying Rydberg states of He4

SCF and CEPA calculations are applied to study the structure of small He cluster ions, He _n ⁺ ,n=2, 3, 4, 5 and some low-lying Rydberg states of He₄. The effect of electron correlation upon the equilibrium structures and binding energies is discussed. He ₃ ⁺ has a linear symmetric equilibrium geometry with a bond length of 2.35a ₀ and a binding energyD _e =0.165 eV with respect to He ₂ ⁺ +He (experimentally:D ₀=0.17 eV which corresponds toD _e ≈0.20 eV). He ₄ ⁺ is a very floppy molecular ion with several energetically very similar geometrical configurations. Our CEPA calculations yield a T-shaped form with a He ₃ ⁺ centre (R _e = 2.35a ₀) and one inductively bound He atom (4.39a ₀ from the central He atom of He ₃ ⁺ ) as equilibrium structure. Its binding energy with respect to He ₃ ⁺ +He is 0.031 eV. A linear symmetric configuration consisting of a He ₂ ⁺ centre with a bond length of 2.10a ₀ and two inductively bound He atoms (4.20a ₀ from the centre of He ₂ ⁺ ) is only 0.02–0.03 eV higher in energy. We expect that in larger He cluster ions structures with He ₂ ⁺ and He ₃ ⁺ centres andn?2 orn?3 inductively bound He atoms have nearly the same energies. In He₄ a low-lying metastable Rydberg state (³ Π symmetry for linear He ₄ ^* ,³ B ₁ for the T-shaped form) exists which is slightly stronger bound with respect to He ₃ ^* +He than the corresponding ion.     

Ab initio calculation of the vertical excitation energies of small helium cluster ions

Quantum chemical ab initio calculations have been performed for the vertical excitation energies and oscillator strengths of all low-lying electronically excited states of small helium cluster ions, He _n ⁺ ,n=2, ..., 7. The geometrical structures of the ions were fixed at the equilibrium geometries of the respective ground states, for He ₄ ⁺ and He ₅ ⁺ also one alternative structure was considered. The low-lying excited states can be classified into two categories: the electronic transition can occur either within the central He ₂ ⁺ or He ₃ ⁺ unit or from the peripheral weakly bound He atoms to this unit. The latter transitions are very weak (f≈0.001), closely spaced, with vertical excitation energies of about 5.7 eV. The He ₂ ⁺ and He ₃ ⁺ units have strong transitions at 9.93 and 5.55 eV, respectively; these transitions are only slightly blue-shifted if He ₂ ⁺ or He ₃ ⁺ are placed as “chromophores” into the centre of a larger He _n ⁺ cluster. The large difference in the vertical excitation energy of the strong transition should enable an experimental decision of the question whether the cluster ions have He ₂ ⁺ or He ₃ ⁺ cores.     

Measurement of state-to-state rotational transfer rates in collision of I2*(B 0u+, υ = 15, j) with 3He, 4He,Ne, Ar,H2, D2 and I2

The selective laser excitation and induced fluorescence observation technique has been used to study rotationally inelastic collisions of I₂^*(B 0_u⁺, υ = 15,j) with I₂, ³He, ⁴He, Ne, Ar, H₂ and D₂. For each collision partner, several initial rotational levels ranging from j_i = 12 up to j_i = 146 have been excited. For purely rotational transfer within the υ = 15 level, our data are perfectly consistent with energy sudden (eventually corrected) scaling laws. Thus, any thermally averaged rate constant, k(j_i → j_f), can be expressed as a function of the basis rate constants k(l → 0). Furthermore, these k(l → 0) are found to follow simple empirical fitting laws. Consequently any k(j_i → j_f) can be predicted given a set of two or three fitting parameters. Collisions with relatively heavy particles (I₂, Ar and Ne) are well described by using the inverse power fitting law k(l → 0) = b[l(l+1)]^?γ, where b = 1.7, 1.2 and 1.2×10^?10 cm³ s^?1 and γ = 1.08, 1.02 and 1.17 for I₂^*-Ne, I₂^*-Ar and I₂^*-I₂ collisions respectively. For collisions with light particles (³He, ⁴He, H₂ and D₂), k(l → 0) shows a sharp decrease with l which can be accounted for by a hybrid power-exponential fitting law k(l → 0) = b[l(l+1)]^?γ exp[-l(l+1)/l^* (l^*+1)], where b = 0.84, 0.71, 2.77 and 2.78×10^?10 cm³ s^?1l⁺ = 20.6, 23.1, 18.8 and 31.4, and γ = 0.66, 0.66, 0.78 and 0.91 for I₂^*-³He, I₂^*-He, I₂^*-H₂ and I₂^*-D₂ collisions, respectively. We confirm that the rotational transfer dynamics in heavy molecules is mainly governed by angular momentum exchange.     

Quantum dynamics of electron capture process during H–He<Superscript>2+</Superscript> collision

Quantum dynamics of electron transfer (capture) phenomenon during the H–He²⁺ collision is investigated by solving two-dimensional time-dependent Schrödinger equation numerically using a third-order split operator technique. Results of this study, represented as the snapshots of the electron wavepacket time evolution, show significantly different dynamics for the electron of different initial orbitals (1s, 2s, 2p _x and 2p _y ) of the incoming hydrogen atom. This electron transfer dynamics is also detailed by calculating expansion coefficients of the projection of the evolving wavepacket onto the stationary eigenfunctions of the H and He⁺ species to investigate evolution of the electron density around each nucleus during the collision. The instantaneous and overall electron densities captured by the He²⁺ nucleus from the H atom are calculated and analyzed. It is also shown evidently and concluded that due to its quantum nature, electron crawls from one nucleus to the other in an electron transfer process during an atom–ion collision.     

CAS SCF/CI calculations of potential energy surfaces of He3+ and He2+

Complete active space MC SCF (CAS SCF) calculations followed by second-order configuration interaction (SOCI) calculations are carried out on the potential energy surfaces (bending surface, linear surfaces) of the ²Σ_g⁺ ground state of He₃⁺. The potential minimum for the ²Σ_g⁺ state occurs at a linear geometry with HeHe bond length of 1.248 Å. The binding energy of He₃⁺ with respect to He + He⁺ + He was calculated to be 2.47 eV at the SOCI level. The energy required to dissociate He₃⁺ (²Σ_g⁺) into He₂⁺ (²Σ_u⁺) and He(¹S) is calculated to be 0.14 eV. The same level of SOCI calculations of He₂⁺ yield a D_e value of 2.36 eV.     

Luminescence in near-thermal charge exchange. III. CH(+) and CD(+) A → X emission from He+ C2H2 and He+ + C2D2

A pulsed ICR cell fitted with synchronous photon counting equipment is used to investigate the emission produced between 185 and 500 nm by near-thermal charge exchange between He⁺ and C₂H₂ (C₂D₂). The emission bands observed are A ²Δ → X²π and (weakly) B²Σ^? → X²π in CH(CD) and A ¹π → X¹Σ in CH⁺(CD⁺). Wavelength measurements on the bandheads of the (0,0) and (0,1) bands of CD⁺ A → X are used to evaluate vibrational constants of CH⁺(CD⁺) X¹Σ⁺. The results are (in cm^?1): ω_e = 2869 ± 27 (2106 ± 20); ω_eχ_e = 65 ± 13 (35 ± 7). These constants are used to calculate Morse-potential Franck—Condon factors and vibrational branching ratios for CH⁺ and CD⁺ A → X emission. The spectral distributions and the (relatively low) absolute emission rates produced by He⁺/C₂H₂(C₂D₂) charge exchange are briefly discussed in the light of presently available information on the charge transfer reaction and on the excited states of C₂H_2?⁺