Measurements of differential cross sections for vibrational quantum transitions in scattering of Li+ on H2

A pulsed monoenergetic ⁷Li⁺ ion beam (lab. energy 10–40 eV) is scattered from a highly collimated (= 1.5°) H₂ nozzle beam. The time-of-flight spectrum of the ions scattered in the forward laboratory direction shows both a fast peak corresponding to forward center-of-mass scattering and a slow peak corresponding to wide-angle center-of-mass scattering. These peaks have been further resolved to show contributions from individual vibrational quantum transitions. From an analysis of the time-of flight spectra the differential inelastic cross sections for a wide range of angles and energies between 2 eV <E_cm < 9 eV have been determined. The spectra also contain information on rotational inelastic cross sections.     

Semiclassical calculation of energy transfer in polyatomic molecules. V. Differential cross sections for excitation of CO2 and N2O colliding with Li+ at E ≈ 4.72 eV

A semiclassical model has been used to calculate differential cross sections for vibrational excitation of CO₂ and N₂O at the center of mass collision energy E≈ 4.72 eV. Also the average rotational excitation as a function of the scattering angle is reported. Comparison is made with experimental data and previous more approximate theoretical calculations.     

Time-dependent close coupling for vibrational excitation in three dimensions: Application to H+ - H2

Impact parameter calculations for the non-reactive H⁺ + H₂ (n_i = 0) → H⁺ + H₂ (n_f) collision are reported for energies 10 eV ? E_cm ? 200 eV describing the rotational motion of the molecule in the sudden limit. The time-dependent Schrödinger equation for the vibrational motion has been solved by close coupling techniques expanding the vibrational wavefunction into both harmonic and numerically exact H₂ bound states. The convergence in vibrational basis sets, where up to six vibrational levels are considered, becomes worse with decreasing energy and increasing inelasticity. Furthermore, the harmonic wavefunctions are not suitable over a large range of energies to calculate proper cross sections. The various integral and differential cross sections have been compared with the classical results of Giese and Gentry.     

Total cross sections for K + Br2 at relative energies between 0 and 8000 eV

Trajectory Surface Hopping (TSH) calculations have been applied to the non-elastic scattering in the K + Br₂ collision system over a wide range of relative kinetic energies from 0 to 8000 eV. Absolute total cross sections have been computed for the formation of various collision products with an accuracy of 5% with respect to statistical errors. The following non-elastic processes have been studied: chemical reaction, inelastic neutral scattering, neutral dissociation and ion pair formation, yielding atomic as well as molecular negative bromine ions together with PC ions. The absolute values of the respective total cross sections, obtained from the TSH calculations, are in close agreement with the available experimental data, both for chemical reaction and for ion pair formation, over the whole energy range considered. The three particle character of the collision system is important in describing the experimental results quantitatively at relative kinetic energies below 100 eV.     

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.     

Differential cross section measurements of rainbow structure in Li+-Ar,Kr and Xe

The differential elastic cross sections (θ_lab < 20°) for Li⁺-Ar, Kr, Xe have been measured for 3 <E_c.m. < 9 eV and compared with those predicted from the electron gas theory of Gordon and Kim for closed shell systems. The experimental well depths are typically deeper than predicted by theory. The largest discrepancy of 9% was found for Li⁺-Kr.     

Measurements of differential cross sections fore-Ar,Kr, Xe scattering atE = 0.05 − 2 eV

Differential scattering experiments have been performed for the systemse-Ar, Kr, Xe in the energy rangeE=0.05 ? 2 eV and the angular range ?=20–100° using a crossed-beam arrangement. The measurements cover the region of the Ramsauer-Townsend minimum (for the first time in differential scattering using modern techniques) and show the drastic variation of the cross section over this energy range. For these experiments, a new electron spectrometer has been developed which is especially designed to allow measurements at very low collision energies under well controlled conditions. In the present work, the measurements could be extended down to 50 meV. The energy resolution was ΔE = 10 meV (FWHM). Absolute cross sections and the correct transmission properties of the systems are determined usinge-He scattering as a reference system. The experimental data are analysed by the MERT method which allows to extrapolate the cross sections to zero energy. On the basis of the MERT parameters, detailed comparison is made with other work.     

Dissociation of ethane by electron impact

The absolute total dissociation cross section for ethane is reported for electron energies between 10 and 600 eV. A maximum value of 7.6 × 10^?16 cm² occurs at 80 eV while the apparent threshold is ≈ 10 eV. Dissociative ionization is more probable than dissociation into neutral fragments at all energies except in the threshold region. The data indicates that fragmentation involving methane elimination (c^? + C₂ H₆ → e^? + CH₄ + CH₂) occurs in less than 2% of the dissociative events for 50 < E < 600 eV. Arguments are presented which suggest that some of the lower excited states of ethane are stable against dissociation.     

Formation of WF−6 and its dissociative products by collisional ionization

The formation of negative ions in electron transfer reactions between hyperthermal alkali atoms (Na, K) and WF₆ has been studied in the energy range 0–30 eV c.m. Relative cross sections and translational energy thresholds for ion pair formation have been measured, from which the following electron affinities (EA) and bond dissociation energies (D) have been derived: EA(WF₆) = 3.7 eV, EA(WF₅) = 1.25 eV, D(WF₅—F) = 5.1 eV, D)WF₅—F^?) = 5.4 eV, D(WF^?₅—F) = 7.6 eV. Several ion molecule reactions are discussed which result in formation of secondary fragmentation ions and WF^?₇.     

Multiple scattering theory. II. Collision induced dissociation in first order

Computationally tractable formulae for one particle differential cross sections and for coincidence cross sections for atom— diatom collision induced dissociation (CID) are obtained within the framework of first order multiple scattering theory. The first order formulation is then used to analyze the simple “knockout circle” model for CID and to derive a more reliable multiple scattering spectator model. Finally, differential and coincidence cross sections are computed for Li⁺ + H₂ at 2O eV and are compared with experiment. The qualitative insight afforded by coincidence studies of CID is clearly demonstrated.     

Complex formation in proton—D2 collisions

Classical trajectory calculations are used to compute the formation cross section (suitably defined) for strongly interacting collision complexes formed in H⁺ + D₂ collisions in the kinetic energy range from 0.1 to 4 eV. This cross section corresponds to the usual Langevin cross section only if the kinetic energy is less than 0.2 eV, and provided that little initial excitation is present, while for higher kinetic energies it drops exponentially. It is in much better agreement with absolute integral cross sections observed experimentally than the latter. Further study shows that it is the contribution from large orbital anglular momenta, which the Langevin cross section overestimates. Orbiting complexes (of H⁺ around D₂) play a negligible role, and are very short-lived. The lifetime of strongly coupled complexes is estimated to be 450 E^?1.3 fs, where E is the total energy in eV. The use of trajectory data to improve Light's phase space theory is discussed.     

Neutral scattering and vibrational excitation in K+Br2 Collisions

Differential cross sections are presented for neutral scattering of K atoms in collisions with Br₂ molecules in the energy range from 20 to 150 eV. In addition energy-loss spectra for the scattered K atoms are shown. The differential cross sections show a large peak near the forward direction. The energy-loss spectra point to considerable vibrational excitation at small angles. The results are attributed to reneutralization from an ion-pair state formed during the collision. In some cases this process can involve three potential surface crossings. The experimental results can be reproduced in simple trajectory calculations on diabatic potential surfaces. The calculations show that the forward scattering is rainbow scattering, caused by the internal motion of the Br₂^? molecular ion during the collision. There is no analog to this rainbow in atom-atom scattering. The internal moti is also responsible for the observed vibrational excitation.     

Molecular-beam study of the K + CF3I reaction at collision energies up to 1.14 ev (c.m.)

Detailed differential cross sections of the K + CF₃I reaction have been measured at collision energies of 0.54 and 1.14 eV (c.m.) and transformed i     

Stereodynamics of O(3P)+H2 at Scattering Energies of 0.5, 0.75, and 1.0 eV

Quasiclassical trajectory calculation of the title reaction O(³P)+H₂→OH+H at three different scattering energies of 0.5, 0.75, and 1.0 eV on the lowest electronic potential energy surface 1³A" has been done. Distribution P(θ_r) of polar angles between the relative velocityk of the reactant and rotational angular momentum vector j' of the product, distribution P(φr) of the azimuthal as well as dihedral angles correlating k-k'-j', 3-dimensional distri-bution, and polarization-dependent differential cross sections (PDDCSs)dependent upon the scattering angle of the product molecule OH between the relative velocity k of the reactant and k' of the product at different scattering energies of 0.5, 0.75, and 1.0 eV are presented and discussed.     

Ion pair formation in alkali-SF6 collisions: Dependence on collisional and vibrational energy

The dependence of ion pair formation in collisions of fast alkali atoms (K, Na and Li) with SF₆ on the initial relative kinetic energy and the internal energy of the target molecule has been studied by the crossed molecular beam method. Using a mass spectrometer we have measured total cross sections for negative ion formation as a function of translational and internal energy. Collision energies ranged from threshold up to 35 eV and SF₆ source temperatures were varied from 300 K to 850 K.By means of an inverse Laplace transform of the measured cross sections, we have determined total specific cross sections for each negative ion depending on the SF₆ vibrational energy and at fixed relative kinetic energy.The relative importance of both collisional and internal energy in promoting the electron transfer process is discussed for the various reaction channels in terms of a collision model. An essential feature of this model is the stretching of the S-F molecular ion bond during the collision. The product show complete relaxation in the threshold region, i.e., vibrational and collisional energy are equivalent: This holds for the SF⁻₆ formation only near threshold and for the SF⁻₅ and F⁻ formation up to about 2 eV above threshold. In the post-threshold region the effect of the internal energy on the cross section dominates over that of the translational energy.From these measurements the adiabatic electron affinity of SF₆ is inferred to be 0.32 ± 0.15 eV, T = 0 K. Some other thermodynamic data are deduced: EA(SF₅) > 2.9 ± 0.1 eV (T = 300 K) and D₀(SF⁻₅-F) = 1.0 ± 0.1 eV.     

Semiclassical calculation of energy transfer in polyatomic molecules. IX. Cross sections for M + CO2 (000) → M + CO2(nml) (M = He and Ar)

Cross sections for excitation of the asymmetric-stretch vibrational manifold of CO₂ in collision with He and Ar have been calculated using a semiclassical collision method and a potential-energy surface constructed from self-consistent field data. The cross sections for collisional energies up to 2.0 eV are compared with those obtained in a molecular-beam experiment.     

Investigation of the B2Σ and test of the A2II interaction potential for Na(32P)-Ar from high-resolution differential scattering measurements

We have measured differential cross sections for scattering of laser-excited Na(3²P_{$\text{3}\text{2}$}) by Ar(¹S₀) at thermal collision energies with high angular resolution (0.1°). In the investigated range of scattering angles (1°–15°) the cross sections contain contributions from scattering along the excited state B²Σ potential (rainbow scattering) and the A²II potential (supernumerary rainbows). By performing fit calculations in which the spectroscopically determined A²II potential was adopted we were able to obtain information about the B²Σ potential. With the assumption of a Lennard-Jones (12.6) potential shape we obtain a well depth ?^BΣ = (0.14±0.02)×10^?3 au and an equilibrium distance r_m^BΣ = 10.4±1.0 au. This work presents the first experimental determination of the B²Σ potential well parameters.     

Production of O− from CO2 by dissociative electron attachment

Dissociative electron attachment cross-section measurements for the production of O^? from CO₂ have been performed utilizing a crossed target-beam—electron-beam collision geometry and a quadrupole mass spectrometer. The relative flow technique is employed to determine the absolute values of cross sections. The attachment energies corresponding to the five cross-section maxima are: 4.4 ± 0.1, 8.2 ± 0.1, 13.0 ± 0.2, 16.9 ± 0.2 and 19.4 ± 0.2 eV. The cross sections at these maxima are: 1.43 × 10^?19 cm², 4.48 × 10^?19 cm², 8.1 × 10^?21 cm², 8.1 × 10^?21 cm² and 1.2 × 10^?20 cm², respectively.