Electron impact ionization of atomic hydrogen

The role of Coulomb-correlation in electron impact ionization of atomic hydrogen is investigated. Triple differential cross sections are calculated using the first order multiple scattering theory taking into account the propper asymptotic behaviour of the final state wavefunction. A semi-empirical procedure is outlined to choose the effective charges consistent with several physically required limits. A comparison with recent experimental data is made; the observed agreement strongly suggests the importance of asymptotic Coulomb-correlation in ionization even at high energies. The first order approximation used here for the hydrogen case is easily generalizable for ionization of several electron atoms at not too large scattering angles and not too low incident energies.     

An improved Born approximation for the electron impact ionization of atomic hydrogen

A two-electron continuum wave function satisfying exact asymptotic boundary conditions (see [1]) is simplified in the high energy limit for asymmetric kinematics. The long range correlation between the fast escaping electron and the target atom in a low continuum state is properly taken into account, and corrects therefore the major shortcoming of the ordinary Born approximation. This improved Born approximation has been employed to calculate triply differential ionization cross sections at intermediate energies.     

Electron impact ionization of haloalkanes in helium nanodroplets

Electron impact (EI) mass spectra of a selection of C1-C3 haloalkanes in helium nanodroplets have been recorded to determine if the helium solvent can significantly reduce molecular ion fragmentation. Haloalkanes were chosen for investigation because their EI mass spectra in the gas phase show extensive ion fragmentation. There is no evidence of any major softening effect in large helium droplets ( approximately 60 000 helium atoms), but some branching ratios are altered. In particular, channels requiring C-C bond fission or concerted processes leading to the ejection of hydrogen halide molecules are suppressed by helium solvation. Rapid cooling by the helium is not sufficient to account for all the differences between the helium droplet and gas phase mass spectra. It is also suggested that the formation of a solid "snowball" of helium around the molecular ion introduces a cage effect, which enhances those fragmentation channels that require minimal disruption to the helium cage for products to escape.     

Recombination of silicon ions by electron capture from atomic hydrogen and helium

 Ab initio potential-energy curves and coupling matrix elements of the Σ and Π molecular states involved in the collision of the Si²⁺, Si³⁺ and Si⁴⁺ multicharged ions on atomic hydrogen and helium have been determined by means of configuration interaction methods. The total and partial electron capture cross sections have been determined using a semiclassical or a quantal approach in the 0.002–0.1 au velocity range. A detailed comparison with very recent theoretical and experimental rate coefficient results is made. Received: 14 September 1999 / Accepted: 3 February 2000 / Published online: 2 May 2000     

Pulsed discharge helium ionization detector

Summary A pulsed discharge helium ionization detector (PDHID) (patent pending) for gas chromatography has been developed. This detector uses a non-radioactive pulsed high voltage discharge source for generation of electrons and pulsed collection of these electrons. We have evaluated this detector for the analysis of a wide range of chemical compounds. In this paper the analytes are passed through the discharge since the permanent gases are difficult to ionize. The initial results for the permanent gases indicate that the PDHID can be used as a universal detector of contaminant traces at detection levels on the order of 1–20 pg. The response in this mode of operation is linear over four orders of magnitude.Dedicated to Professor Leslie S. Ettre on the occasion of his 70th birthday.     

Determination of atomic hydrogen in non-thermal hydrogen plasmas by means of molecular beam threshold ionization mass spectrometry

Atomic hydrogen plays important roles in chemical vapor deposition of functional materials, plasma etching and new approaches to chemical synthesis of hydrogen-containing compounds. The present work reports experimental determinations of atomic hydrogen near the grounded electrode in medium-pressure dielectric barrier discharge hydrogen plasmas by means of molecular beam threshold ionization mass spectrometry (MB-TIMS). At certain discharge conditions (a.c. frequency of 24 kHz, 28 kV of peak-to-peak voltage), the measured hydrogen dissociation fraction is decreased from approximately 0.83% to approximately 0.14% as the hydrogen pressure increases from 2.0 to 14.0 Torr. A simulation method for extraction of the approximate electron beam energy distribution function in the mass spectrometer ionizer and a semi-quantitative approach to calibrate the mass discrimination effect caused by the supersonic beam formation and the mass spectrometer measurement are reported.     

Detection of atomic hydrogen in flames by resonance four-photon ionization at 365 nm

The first observations of the four-photon ionization of H atoms at 364.7 nm via a three-photon resonance on the Lyman alpha transition are reported. The resonance ionization detection of H and D atoms in an H₂/D₂/O₂/Ar flame is demonstrated and H-atom density profiles are measured with good spatial resolution. A broadening of 2.2 cm⁻¹ /GW cm² of the four-photon resonance by ac Stark shifting is observed.     

Electron impact ionization in helium nanodroplets: controlling fragmentation by active cooling of molecular ions

Reported here is a study of the effects of liquid helium cooling on the fragmentation of ions formed by electron impact mass ionization. The molecules of interest are picked up by the helium nanodroplets as they pass through a low pressure oven. Electron impact ionization of a helium atom in the droplet is followed by resonant charge transfer to neighboring helium atoms. When the charge is transferred to the target molecule, the difference in the ionization potentials between helium and the molecule results in the formation of a vibrationally hot ion. In isolation, the hot parent ion would undergo subsequent fragmentation. On the other hand, if the cooling due to the helium is fast enough, the parent ion will be actively cooled before fragmentation occurs. The target molecule used in the present study is triphenylmethanol (TPM), an important species in synthetic chemistry, used to sterically protect hydroxyl groups. Threshold PhotoElectron PhotoIon COincidence (TPEPICO) experiments are also reported for gas-phase TPM to help quantify the ion energetics resulting from the cooling effects of the helium droplets.     

Determination of antiproton mass from the calculation of energy levels of antiprotonic helium atoms

We calculate the energy levels of the metastable states of an antiprotonic helium atom. The coupled rearrangement channel method is employed to describe a dual character of the atom effectively. Calculated transition frequencies between the metastable states are in good agreement with the observed values. The uncertainty of an antiproton mass is estimated by the calculated transition frequencies with the slightly shifted antiproton mass from the proton mass. When a more accurate value of the charge-to-mass ratio of antiproton is considered, the uncertainty of antiproton mass and charge is estimated at 54 ppb which improves the value recommended by the particle data by a factor of ten.     

Reactions of atomic nitrogen and atomic hydrogen with methylacetylene

The reaction of nitrogen atoms with methylacetylene has been studied using a fast-flow low-pressure reactor coupled to a mass spctrometer by a nozzle-beam sampling system. Hydrogen atom concentrations were measured by ESR analysis. Experimental second-order rate constants for the consumption of N atoms, of C₃H₄, and for the formation of N₂ were determined in the temperature range of 283° to 485°K. Product profiles of all stable species and of hydrogen atoms and methyl radicals were obtained for different initial concentrations of the reactants. Two different reaction pathways can be distinguished: one provides for recombination of N atoms, and the second leads to the formation of cyano compounds and other hydrocarbons. Only the latter process is influenced by the addition of hydrogen atoms. Mechanisms for the two pathways are discussed.     

Empirical regularities of atomic ionization potentials

Regularities of the averaged ionization potentials for atoms and ions containing up to 18 electrons are studied in detail. It is shown that a two-variable function constructed from the averaged ionization potentials for each subshell is linear with respect to the degree of ionization q and the occupancy k of the s^k or p^k subshell. One linearity includes previous findings as a special case, and the other introduces a new regularity for atomic ionization potentials. Existing atomic ionization potentials and electron affinities are analyzed employing the regularities, and improved values of these quantities as well as term and fine structure separations in negative ions are derived.     

Laser-assisted electron-impact excitation of hydrogen and helium atoms

The excitation of H(1s–2s) and He(1¹ S–2¹ S) by electron impact in the presence of a nonresonant laser field is studied in the framework of the perturbation theory. The wavelength variation of the total cross section is presented at incident electron energies of 100 eV and 200 eV for hydrogen and 200 eV for helium. The use of pseudostates as intermediate states in the study of excitation of hydrogen is also investigated.     

Isotopic quadrupole mass spectrometry of hydrogen and helium

Analysis of isotopes of hydrogen and helium without radioactive components by quadrupole mass spectrometry (QMS) has been investigated for measuring the purity of deuterium for injection into the Tokamak of Strong Field. External radioactive source²⁴Na is used to imitate accompanying ionizing radiation of T₂. A threshold magnitude of exposure dose power is found, the exceeding of which leads to the increase of detection limit and systematic errors of isotopic analysis. QMS is used at medium resolution of 300 to determine compositions of³He in HD/H₃ and⁴He in D₂/H₂D, and to quantify impurities in the mass range from 1 to 22 amu. Analysis of⁴He–D₂ mixtures demonstrates the capability to measure isotopic composition with accuracy from 0.2 to 0.5%, depending on the samle-to-reference ratio of inlet pressure.     

Spectroscopy of nonspherical atomic bubbles in solid helium

We analyze the effect of the host crystal symmetry on the optical spectra of the 6P(1/2)-6S(1/2) and 6P(3/2)-6S(1/2) transitions of atomic Cs in solid (4)He matrices. In particular, we address the deformation of the bubble structures formed by Cs in such quantum crystals. We show that the anisotropy of the stiffness tensor leads to static quadrupolar bubble shape deformations in hexagonally close-packed (hcp) crystals, while the corresponding deformations in the body-centered cubic (bcc) phase of the matrix have a hexadecupolar symmetry. A comparison of the measured excitation spectra with our model calculations allow us to infer quantitative values of the deformation parameters.     

One photon double ionization of helium: threshold behaviour

In order to study the dynamics of double photoionization of helium, we report new coincidence measurements between low energy electrons and doubly charged ions, from 78 to 95 eV photon energy. We show that the range of validity of the Wannier theory depends upon the observable. For the exponentn of the threshold law, this range amounts to some 3 eV above onset, thus confirming previous published experimental work. In contrast, the energy distribution of the two outgoing electrons is found flat, within 20%, in agreement with the theoretical predictions, but in a 15 eV energy range above threshold.     

Core-shell effects in the ionization of doped helium nanodroplets

Core-shell particles with water clusters as the core and surrounded by an atomic or molecular shell have been synthesized for the first time by adding water and a co-dopant sequentially to helium nanodroplets. The co-dopants chosen for investigation were Ar, O(2), N(2), CO, CO(2), NO and C(6)D(6). These co-dopants have been used to investigate the effect of an outer shell on the ionization of the core material by charge transfer in helium nanodroplets. The specific aim was to determine how the identity of the shell material affects the fragmentation of water cluster ions, i.e. whether it helps to stabilize parent ion ((H(2)O)(n)(+)) formation or increases fragmentation (to form (H(2)O)(n)H(+)). N(2), O(2), CO(2) and C(6)D(6) all show a marked softening effect, which is consistent with the formation of a protective shell around the water cluster core. For CO and NO co-dopants, the response is complicated by secondary reactions which actually favour water cluster ion fragmentation for some water cluster sizes.     

氦离子化气相色谱仪校准用混合物中甲烷气体标准物质研制

介绍氦中甲烷气体标准物质的制备方法.以超纯氦气和高纯甲烷为原料,采用称量法制备特性值为10μmol/mol的氦中甲烷气体标准物质.采用气相色谱法(DID检测器)对制备的标准物质进行均匀性、稳定性检验,并对定值结果的不确定度进行评定.研制的气体标准物质均匀性和稳定性良好,有效期为12个月,相对扩展不确定度为2％(k=2)...