A contribution to the study of the influence of metastables in the flowing afterglow plasma

The paper describes an experimental apparatus based on the flowing afterglow technique which enables the study of the role of metastable atoms of the carrier gas by means of titration of the reactant vapour of gas into the flow tube. A study of the behaviour of the electron and ion density and electron distribution of Ar* metastables (Ar as the carrier gas) using Penning ionization of the ethyl alcohol (CH₃CH₂OH) (titration vapour) has been made by means of a described experimental set-up. The method of estimation of the metastables concentration in the decaying flowing afterglow plasma by Langmuir probe technique with use of titrant technique is also studied.     

The Influence of Collisions in the Space Charge Sheath on the Ion current Collected by a Langmuir Probe

The current/voltage characteristics of a cylindrical Langmuir probe have been studied in Ar⁺/electron afterglow plasmas in helium carrier gas under truly thermal conditions at 300 K using our flowing afterglow/Langmuir probe (FALP) apparatus. The orbital motion limited (oml) ion and electron current regions of the probe characteristics have been explored over a wide range of the reduced probe voltage (up to ～ 100) and over a wide range of electron (n_e) and ion (n₊) number densities (1.6 × 10⁷ to 1.5 × 10¹⁰ cm^?3) at a constant pressure of the He carrier gas of 1.2 Torr. The observed increase of the probe ion currents above those predicted by collisionless oml theory, resulting in an apparent increase of the measured ion number density above n_e in the plasma, is explained by the enhancement in the ion current collection efficiency due to collisions of ions with neutral gas atoms in the space charge sheath surrounding the probe. The continuous change in the exponent, χ, of the power-law dependence,i₊ ∞ V of the ion current, i₊, on the probe voltage, V_p from 0.5 at the highest n₊ (smallest sheath) towards 1.0 at the lowest n₊ (large sheath) indicates that the ion current collection from the plasma changes from the oml current regime at the high n₊ to the continuum regime at the low n₊ when the ions undergo multiple collisions with the helium atoms in the space charge sheath and thus “drift” towards the probe.     

The Influence of Ion – Neutral Collisions in the Plasma Sheath on the Ion Current to an Electrostatic Probe: Monte Carlo Simulation

We have carried out Monte Carlo simulation of the motion of Ar⁺ ions in the space charge sheath surrounding a cylindrical Langmuir probe. From these simulations the percentage of ions crossing the sheath boundary that are collected by the probe have been determined and thus the ion currents to the probe have been calculated. It is shown that the collisions of ions with neutral helium gas atoms in the sheath increase the percentage of ions collected by the probe above that predicted by collisionless orbital motion limited current (OMLC) theory and that the exponent, χ, of the power law dependence, i₊～U, of the ion current, i₊, on the probe voltage, U_p, increases above the value 0.5 predicted by OMLC theory. The results of the simulations are compared with recent Langmuir probe measurements made in flowing afterglow plasmas.     

Ion-molecule reactions at thermal energies

Ion-molecule reactions is a generic word for reactions involving ions (both positive and negative), radicals and stable neutrals. In this presentation, use of the flowing afterglow technique to study ion-molecule reactions at thermal energies is demonstrated using the examples of positive ion-negative ion mutual neutralization of molecular nitrogen ion (N ₂ ⁺ ) with F⁻ and the reaction of atomic nitrogen with SF _n (n=1 to 5) to form NF.     

Monte Carlo Simulations of the Influence of Ion‐Neutral Collisions on the Ion Currents Collected by Electrostatic Probes

We have carried out Monte Carlo simulation of the motion of Ar⁺ ions in the space charge sheath surrounding a cylindrical Langmuir probe. The ion currents to the probe have been calculated from these simulations and the percentages of ions crossing the sheath boundary that are collected by the probe have been determined. It has been shown that the collisions of ions with neutral helium gas atoms in the sheath increase the percentage of ions collected by the probe above that predicted by collisionless orbital motion limited current (OMLC) theory at lower helium pressure and decrease this percentage below the OMLC theory prediction at higher helium pressure. It has been shown also that the ion current almost does not depend on probe radius at higher helium pressures. The results of the simulations have been compared with recent Langmuir probe measurements made in flowing afterglow plasmas and with other probe theories.     

Experiments on the sputtering of neutral Cu2 dimers from Cu by Ar+ ions (60–300 eV)

A planar polycrystalline copper target was bombarded normally by Ar⁺ ions with energies ranging from 60 to 300 eV. in the source of a mass spectrometer. The neutral particles sputtered normally from the target were post-ionized and analyzed in the mass spectrometer. A thermionically sustained, magnetically confined low pressure arc plasma was used to supply the bombarding ions, and for post-ionization of the neutral sputtered species. It was found that the relative yields of the sputtered neutral post-ionized Cu₂ dimers are linearly proportional to S², where S is the total sputtering yield for Ar⁺ -Cu. The results support the recombination model for the formation of neutral dimers in sputtering.     

Mass spectrometer studies of the ion composition in the pink afterglow

The time dependences of the ion number densities in the pink afterglow of nitrogen, as represented by the ion wall currents, have been measured. The ions were extracted through an orifice from a flow system and analysed by a quadrupol mass spectrometer. It has been found thatN ₂ ⁺ ions are dominating in the early afterglow. With the beginning of the ionization processN ₃ ⁺ and at pressure >6 TorrN ₄ ⁺ become the majority ions. The ratio of the number densities(N ₃ ⁺ )/(N ₂ ⁺ ) reaches a maximum during the increase of the ionization processes before the maximum is reached. This behaviour suggestsN ₃ ⁺ ions to be the primary ions created by the ionization processes. The time dependences of the ion number densities (N ₂ ⁺ ), (N ₃ ⁺ ) and(N ₄ ⁺ ) are found to vary similar, showing that the ions are strongly coupled by conversion processes. The conversion processes are discussed. In the maximum of ionization at a total pressure of 4.4 Torr the ratios of the number densities of the afterglow ions (N ₂ ⁺ )∶(N ₃ ⁺ )∶(N ₄ ⁺) are 1∶1.9∶0.64.     

Non-Maxwellian electron energy distribution function in He,He/Ar,He/Xe/H<Subscript>2</Subscript> and He/Xe/D<Subscript>2</Subscript> low temperature afterglow plasma

Experimental studies of the electron energy distribution function “EEDF” under well defined conditions in flowing afterglow plasma, using a Langmuir probe are reported. The EEDF is measured in He₂ ⁺ and Ar⁺ dominated plasmas and in XeH⁺ and XeD⁺ dominated recombining plasmas. He is used as a buffer gas at medium pressures in all experiments (1600 Pa, 250 K). The deviation of the measured EEDF from Maxwellian distribution is shown to depend on plasma composition and on the processes governing the plasma decay. The influence of energetic electrons produced during the plasma decay on the body and tail of the EEDF is observed. The mechanism of energy balance in afterglow plasma is discussed.     

New Methods for Fully Automated Isotope Ratio Determination from Hydrogen at the Natural Abundance Level

Abstract

A variety of methods for measurement of ²H/¹H from H₂ are evaluated for their ability to be fully automated and for applicability to automated isotopic analysis of water and organic compounds. Equilibration of water with H₂ gas with the aid of a platinum catalyst has been commercialized into a fully automated sample preparation device. A second and newer technique, involving injecting water, methane, or other volatile organic compounds onto hot chromium in a reactor attached to the dual inlet system of a gas isotope ratio mass spectrometer, can be integrated with a conventional GC-autosampler to allow automated analysis of a variety of substrates. Both techniques result in precisions around 1‰ (δ notation) on the VSMOW scale, and are fast and accurate, and with appropriate mass spectrometers require only negligible scaling for the SLAP/VSMOW difference. Several experimental methods which show considerable promise employ “isotope ratio monitoring” (irm) inlet systems, in which a carrier gas is used for transport of H₂ to the mass spectrometer. Any such method has to address the problem of He ions corrupting the measurement of the H₂ ions. One such approach uses a heated palladium membrane for selective introduction of H₂ into the mass spectrometer, and a second involves modifications to the ion optics to control the stray helium ions. Both approaches have significant limitations that must be overcome before irm techniques can be used in routine applications, in particular for measuring hydrogen isotopes from GC effluents (irm-GCMS).     

The measurement of energy spectra of neutral particles in low energy ion scattering

An apparatus is described for low energy (0.1–10 keV) ion scattering (LEIS) experiments. A time of flight (TOF) spectrometer is incorporated in the system to be able to measure the energy of particles in the neutral state after scattering. The energy resolution ΔE/E of the TOF spectrometer is discussed and found to be 0.5% (FWHM). This is sufficient for our scattering experiments. An electrostatic analyzer (ESA) is used to measure the energy of scattered ions [ΔE/E=0.5% (FWHM)]. Experiments show that in general the ion dose needed to obtain a TOF spectrum (2×10¹⁰ ions/cm²) is much smaller than the dose needed for an ESA-spectrum (6×10¹³ ions/cm²). The ion spectra measured with the TOF spectrometer, by subtracting the neutral yield from the total yield, as well as with the ESA are found to agree quite well. This provides a way to calibrate the TOF spectrometer. The determination of the ion fraction of scattered particles is discussed [10 keV⁴⁰Ar⁺ on Cu(100), scattering angle 30°]. It is shown that the TOF spectrometer is able to measure light recoil particles (e.g. hydrogen) from a heavy substrate. In the analysing system is, in addition to the TOF spectrometer, also incorporated a stripping cell to measure the energy of neutral scattered particles. An energy spectrum of neutral scattered particles measured with both methods is shown.     

Isotopic ratio of evaporated ions,critical ionization distances,and ionization regions in the process of the field evaporation of molybdenum at high temperatures

A magnetic mass spectrometer with a field ion source has been used to study the steady-state field evaporation of molybdenum at a temperature of 1000–2000 K. Ions of all seven molybdenum isotopes have been observed in the process of evaporation; only low-charge ions Mo⁺² and Mo⁺ have been detected. The critical ionization distances and ionization regions for single- and double-charge Mo ions have been identified based on the measured ion energies and the experimentally determined intensity of the evaporation field. It has been demonstrated that ions are produced in the process of field evaporation of surface atoms at certain distances from the emitter surface in a very narrow spatial region.     

High resolution laser spectroscopy of metallic atoms and molecules: Storage of singly and doubly charged ions transferred from externally generated laser plasmas

A radio-frequency (RF) ion trap has been constructed for high resolution laser spectroscopy of metallic ions. Ions in externally generated laser plasma have been directly introduced into the RF ion trap. An Nd:YAG laser is used to vaporize and ionize sample metals placed behind a ring electrode. Both hyperbolic and cylindrical electrodes are successfully used for confinement of the ions. Trapped ions are detected either with a quadrupole mass spectrometer or with a photomultiplier for the measurement of laser-induced fluorescence. Metallic ions such as Ca⁺, Ba⁺, La⁺, Nd⁺, Tm⁺, Lu⁺, and Ta⁺ have been confined for the time range of several to 20 minutes in the presence of He buffer gas, and a doubly charged ion Ba²⁺ for several seconds. Some ions like Nd⁺, Lu⁺, Hf⁺, and Ta⁺ are found to be highly reactive with background gaseous molecules.     

Decay reactions of rare gas cluster ions: Kinetic energy release distributions and binding energies

We have carried out measurements on metastable fragmentation of mass selected argon cluster ions which are produced by electron impact ionization of a neutral argon cluster beam. From the shape of the fragment ion peaks (MIKE scan technique) one can deduce information about the distribution of kinetic energy that is released in the decay reaction. In this study, for Ar ₅ ⁺ to Ar ₁₅ ⁺, it is Gaussian and thus we can calculate from the peak width the mean kinetic energy release 〈KER〉 of the corresponding decay reactions. Using finite heat bath theory we calculate from these data the binding energies of the decaying cluster ions. Received 20 November 2000     

Structures and reactions of biomolecular ions produced with electrospray ionization

Photo-induced reaction of [Fe(III)-protoporphyrin]⁺ (hemin⁺) ions solvated with dimethylsulfoxide (DMSO) is investigated by using a tandem mass spectrometer with electrospray ionization. We measure the photodissociation yields of mass-selected hemin⁺(DMSO)_n clusters for n = 0-3. The mass spectra of the fragment ions show the -cleavage of carboxymethyl groups in addition to the evaporation of solvent molecules. Yield of the -cleavage reaction is found to depend strongly on the excitation energy and the number of solvent molecules. We also examine photo-induced reactions of multiply-charged cytochrome c ions, (M + nH)^{n +} ( n = 9-17). Photoionization is found to be the dominant process for the lower charged states ( n = 9-12) and its yield decreases rapidly with increasing the charge. The photoionization is ascribed to the emission of electron by multiphoton excitation of heme under the influence of Coulomb attractive potential arising from the charges in the polypeptide chain. Model calculations of the Coulomb potential suggest that the structure of the polypeptide chain is completely elongated.     

Radiative lifetime measurements of vibrational levels of Cl2 + A 2Π u

The radiative lifetimes of several vibrational levels of Cl₂ ⁺ A ²Π _u are measured by a novel technique. A uniform electric field extracts the ions from the observation region of a spectrometer, and the decrease of fluorescence signal as a function of the electric field strength is measured to obtain the radiative lifetime. Measurements are made on 20 different vibronic bands of the Cl₂ ⁺ A ²Π _u -X ²Π _g system, and the results are compared with other methods. An attempt is made to correlate the results with the highly perturbed spectroscopic nature of the A ²Π _u electronic state.     

Secondary Electron and Negative-Ion Emission from Metal Surface under the Bombardment by Positive Ions (H<Superscript>+</Superscript>, Cl<Superscript>+</Superscript>, HCl<Superscript>+</Superscript>)

A trap for positive ions (H⁺, Cl⁺, HCl⁺) is created within a time-of-flight mass spectrometer. The yields of secondary electrons and negative ions (HCl^?, H^?) formed due to forward and backward scattering of positive ions by steel wire at different kinetic energies (200–750 eV) are measured.     

Low energy (E0 < 10 keV) atom and ion scattering of neon from a Cu(100) surface; Ionization and neutralization

The ion fractions η⁺ of low energy (5–10 keV) neon particles scattered from a Cu(100) surface are measured with a time of flight spectrometer. These fractions are obtained for neutral as well as charged projectiles and for different crystal directions. The scattering angle θ was 30°. For a primary energy E₀ of 5 keV neutral projectiles have a value for η⁺ which is 30 times lower than for charged projectiles; these values are 0.15 and 4.5% respectively. For E₀ = 10 keV the values of η⁺ are about the same (~22%). Energy differences up to 22 eV, depending on E₀, are observed between the single scattering peaks in the ion spectra of charged and neutral projectiles but also between the single scattering peak in the spectra of all scattered particles and of ions, with ions as projectiles. A qualitative discussion of these data is given, involving charge transfer processes of noble gas particle and target atom. The data suggest that these neutralization processes can be described more adequately with interatomic neutralization processes along the trajectory than with Auger neutralization by conduction electrons.     

Optimum ion implantation and annealing conditions for stimulating secondary negative ion emission

The type, energy, ion dose, and heating temperature required to ensure a stable minimum work function of a surface in one experimental cycle (at least 2–3 min) are determined. Secondary ion mass spectrograms are recorded using Cs⁺, Ba⁺, and Ar⁺ ions. Cu, Al, and Mo samples are studied. The optimum ion implantation conditions and the activation temperature that provide a stable minimum work function of the sample surfaces are found. The samples implanted by Ba⁺ ions withstand higher temperature and current loads than the samples implanted by Cs⁺ ions. However, the work function in the case of Cs⁺ ions decreases stronger (to 1.9 eV). It is shown that neutral sputtered particles do not leave the surface at eφ ≤ 1.85–1.90 eV.     

High-resolution mass spectra of the residual gas in a metallic vacuum system

The mass spectra of the residual gas in a metallic vacuum chamber of capacity 3 l are studied with an MI-9303 high-resolution magnetic resonance mass spectrometer in the mass range 1–140 u. The experiments are carried out under four evacuation conditions in the pressure range P = 10⁻⁸–10⁻¹⁰ Torr, and almost all the mass peaks forming multiplets are resolved. It is shown that the multiplets with mass numbers M≤80 have, as a rule, a multicomponent structure and hydrogen is the basic component responsible for the total pressure in the chamber irrespective of evacuation conditions. Next in order of intensity in the mass spectra are, CH ₄ ⁺ , H²O⁺, CO⁺, and CO ₂ ⁺ peaks. Other lines in the residual gas spectra are largely due to various C-, H-, N-, and O-based compounds. In addition, the background mass spectrum involves Cl-and F-based compounds and noble gas isotopes. The multiplets with M > 80 often degenerate into a single hydrocarbon line.     

Determination and analysis of opiates in complex mixtures by surface-ionization mass spectrometry

The results of studies of the analytical opportunities of surface-ionization mass spectrometry (SIMS) for high-sensitivity and selective detection and analysis of opiate mixtures—natural opium, crude heroin, and narcotic analgesic omnopon—are presented. The experiments were carried out using an MX-1320 chemical mass spectrometer modernized for studying surface ionization (SI). It was ascertained that the opiate mixtures are ionized by highly efficient surface ionization. The bands of M⁺ (for papaverine), (M-H)⁺, (M-H-2nH)⁺, (M-R)⁺, and (M-R-2nH)⁺ ions, where M is a molecule, H is a hydrogen atom, R is a radical, are observed in the mass spectra; they are the sum of the SI mass spectra of components of the mixtures. The series of bands of ions with m/z of 144 and 146 that is characteristic of SI-morphinelike molecules is the main one in the mass spectrum of crude heroin, while for omnopon and natural opium this series is the main at low temperatures of a thermionic emitter (up to ∼900 K). At high temperatures of the thermionic emitter, the band series with m/z of 218 and 220 is the main series. Studies of natural opium, crude heroin, and omnopon have shown that the SIMS method allows analyzing mixtures without preliminary chromatographic separation thereof. The study also contains the results of comparative analyses of opiate mixtures by SIMS and chromate- and mass spectrometry (HP-6890) with electronic ionization.