Atmospheric-pressure Penning ionization of aliphatic hydrocarbons

A study has been made of the atmospheric-pressure Penning ionization (APPeI) of aliphatic hydrocarbons (pentane, hexane, heptane, and octane) with long-lived rare gas atoms (Rg*). The metastable rare gas atoms (He*, Ne*, Ar* and Kr*) were generated by the negative-mode corona discharge of atmospheric-pressure rare gases. In the Rg*APPeI mass spectra for aliphatic hyrocarbons, the relative abundances of fragment ions were found to increase in the order of He* --> Ne* --> Ar* --> Kr*. The order is in the opposite direction to the internal energies of the Rg*. The less fragmentation observed for He* may be because the nascent molecular ions [M(+.)]* formed by Penning ionization have lifetimes long enough for them to be collisionally deactivated in the atmospheric-pressure ion source. It was found that the relative abundances of fragment ions in Ar*APPeI increased when the sample pressure in the ion source was reduced. This is attributed to the collision of Ar* with molecular ions followed by fragmentation.     

Formation of doubly positively charged diatomic ions of Mo2(2+) produced by Ar+ sputtering of an Mo metal surface

Long-lived metastable doubly positively charged diatomic ions of Mo2(2+) have been produced by Ar+ bombardment of a molybdenum metal surface. These exotic molecular dications, such as for example 92,95Mo2(2+) at m/z 93.5, could be observed in positive ion mass spectra for ion flight times of approximately 17 micros in a Cameca IMS-3f secondary ion mass spectrometer, when the ion extraction field was adjusted for detection of ions that are formed in the gas phase several micrometers in front of the sputtered surface. Mo2(2+) was observed at high primary current densities for projectile ions of Ar+, but could not be detected under very similar bombarding conditions for projectile ions of Xe+. Such a dependence of ion production by inert gas sputtering on the primary ion species [ionization energies: IP1(Ar) = 15.76 eV and IP1(Xe) = 12.13 eV] is unusual. It is shown that formation of Mo2(2+) dications takes place by resonant charge transfer in grazing gas-phase collisions between incoming projectile ions of Ar+ and sputtered molecular ions of Mo2+. The efficiency for such a resonant electron capture (Mo2+ + Ar+ --> Mo2(2+) + Ar) is of the order of 10(-5) for the bombarding conditions in our mass spectrometer and corresponds to a cross section of a few 10(-15) cm2.     

FTIR analysis of dimethyl ether decomposition products following charge transfer ionization with Ar+ under matrix isolation conditions

Fourier transform infrared spectroscopic analysis has been performed on argon matrices formed following electron bombardment of argon/dimethyl ether mixtures. Products consistent with the ionization and subsequent fragmentation of dimethyl ether cation have been observed. Following ionization of dimethyl ether, fragmentation occurs that is consistent with ionization energy greater than 15 eV due to efficient charge transfer from dimethyl ether to Ar(+) as the major ionization process. Major products observed in the infrared spectra are methane, formaldehyde, HCO(*), CO, and Ar(2)H(+). These products are consistent with the known fragmentation of photoionized dimethyl ether in a 15-16 eV ionization energy range. However, the observation of dehydrogenated products is consistent with additional abstraction of hydrogen from proximally located species isolated within the matrix. Analogous experiments employing CD(3)OCH(3) give similar results, and the observed isotopically substituted products are consistent with the proposed fragmentation pathways.     

Photoionization of helium nanodroplets doped with rare gas atoms

Photoionization of He droplets doped with rare gas atoms (Rg=Ne, Ar, Kr, and Xe) was studied by time-of-flight mass spectrometry, utilizing synchrotron radiation from the Advanced Light Source from 10 to 30 eV. High resolution mass spectra were obtained at selected photon energies, and photoion yield curves were measured for several ion masses (or ranges of ion masses) over a wide range of photon energies. Only indirect ionization of the dopant rare gas atoms was observed, either by excitation or charge transfer from the surrounding He atoms. Significant dopant ionization from excitation transfer was seen at 21.6 eV, the maximum of He 2p 1P absorption band for He droplets, and from charge transfer above 23 eV, the threshold for ionization of pure He droplets. No Ne+ or Ar+ signal from droplet photoionization was observed, but peaks from HenNe+ and HenAr+ were seen that clearly originated from droplets. For droplets doped with Rg=Kr or Xe, both Rg+ and HenRg+ ions were observed. For all rare gases, Rg2+ and HenRgm+ (n,m> or =1) were produced by droplet photoionization. Mechanisms of dopant ionization and subsequent dynamics are discussed.     

Mass spectrometric determination of appearance energies for ions formed from CoF(4) and CoF(3) molecules

Knudsen cell mass spectrometry was applied to the evaluation of the ionization efficiency curves for the ions originating from CoF(4) molecules. Cobalt tetrafluoride was obtained in the gas phase over the CoF(3)(s)-TbF(4)(s) system in the temperature range from 640 to 690 K. From the ionization efficiency curves the appearance energies of the ions formed from the CoF(4) molecules were determined by means of Vogt's deconvolution method. Clausius-Clapeyron plots for the ions from CoF(4) molecules were measured. Evaporation of pure CoF(3)(s) was carried out, and the appearance energies of the ions formed from CoF(3) molecules were determined. The ionization energies for CoF(4) and CoF(3) molecules were found to be (14.3 +/- 0.2) and (13.3 +/- 0.1) eV, respectively.     

Photoelectron resonance capture ionization (PERCI): A novel technique for the soft-ionization of organic compounds

Photoelectron resonance capture ionization (PERCI) is demonstrated as a sensitive ionization technique involving minimal fragmentation of organic molecules. PERCI has been used successfully to softly and efficiently ionize both strongly UV absorbing and non-absorbing molecules. Tunable low energy (<1 eV) electrons are generated by focusing a pulsed UV laser on an aluminum photocathode in the presence of gas phase analyte. Negative ions are formed through a resonance electron capture process. Mass analysis is done using a reflectron time-of-flight mass spectrometer. PERCI is demonstrated for a number of gas phase compounds and simple mixtures, including sulfur hexafluoride, nitrobenzene, nitrophenol, 2-pentanone, hexanal, heptanal, and octanal. In all cases the molecular ion (or [M - H](-)) was observed to be the dominant peak. The 1sigma limit of detection was estimated to be on the order of 10(6) molecules in the ionization region.     

纳秒强光场下呋喃的激光电离中高价离子的产生

The photo ionization of furan by an intense 25 ns Nd:YAG 532 nm laser has been studied by time-of-flight mass spectrometry. At the laser intensity of 1010～1011 W/cm2, multi-charged ions Can+ (n=2～4) and Ohm+ (m=2～3) appeared in the mass spectra when argon was used as the carrier gas. From the peak splitting and the numeric analysis, the most probable kinetic energies of C2+, C3+ and C4+ were confirmed to be 21、63 and 100 eV respectively, and the most probable kinetic energies of O2+ and O3+ were confirmed to be 20 and 40 eV respectively. It is proposed that the multi-charged ions come from the Coulomb explosion of furan cluster ions produced by multi photon ionization of neutral furan cluster.     

Chloride attachment negative-ion mass spectra of sugars by combined liquid chromatography and atmospheric pressure chemical ionization mass spectrometry

A method has been developed for the rapid determination of sugars, including molecular weight measurements, using high-performance liquid chromatography coupled with negative-ion, atmospheric-pressure chemical-ionization mass spectrometry. The chromatography was carried out on a 250 x 4 mm I.D. column packed with 7 microns NH2-silica. The mobile phase consisted of a high percentage of methanol or acetonitrile with a small amount of chloroform. During the mass spectrometry, a strong base is formed from the polar solvent molecules by corona discharge, followed by ion-molecule reactions in the chemical ionization ion source (e.g. the methoxy anion is formed from methanol). This strong base reacts with the chloroform, generating chloride ions, which in turn react with the neutral sugar molecules as they elute from the chromatograph. The chloride ion and sugar interactions yield chloride-attachment ions, which are further stabilized by successive collisions. In this method, authentic monosaccharides and some oligosaccharides show dominant quasi-molecular ions, [M + Cl]-, with little fragmentation, and its particularly useful for the molecular weight determination of sugars.     

The chemistry of ionized Acetone/Ar mixtures under varying gas flow and mole ratio conditions: A matrix‐isolation study

The chemistry of ionized acetone : Ar mixtures under varying total gas flow rate and acetone : Ar mole ratio conditions has been studied using matrix‐isolation techniques. Gaseous acetone diluted in excess argon gas was subjected to electron bombardment with 300‐eV electrons. The products of subsequent reaction processes were matrix isolated and analyzed by Fourier transform infrared (FTIR) absorption spectroscopy. Products included 1‐propen‐2‐ol (the enol isomer of acetone), methane, ketene, carbon monoxide, ethane, ethene, acetylene and tricarbon monoxide. Variations in the total flow rate of gas resulted in changes in the efficiency of product formation without significant changes in the relative amounts of the major species formed. Variations in the acetone : Ar mole ratio at fixed total gas flow resulted in striking variations in the products formed, demonstrating a shift from single acetone molecule‐derived charge‐transfer ionization chemistry at low acetone mole ratios, to processes consistent with the participation of two or more acetone molecules at intermediate mole ratios. These results are interpreted in the context of ion‐molecule reaction processes, the onset of which occurs at intermediate acetone mole ratios. Ethane dehydrogenation products are proposed to result from product secondary ionization, a process that is prevalent at high ionizing electron fluxes. Copyright © 2008 John Wiley & Sons, Ltd.     

Characterization of laser ablation and ionization in helium and argon: A comparative study by time-of-flight mass spectrometry

Laser ablation and ionization in ambient helium and argon gases were studied by multiple-stage time-of-flight mass spectrometry. Measurements made at different gas pressures indicated that there exists an optimal pressure for adequately cooling energetic ions and reducing multiply charged ions that are higher for He than for Ar. The temporal distributions of ions were compared at various laser fluences and gas pressures, and the broad distributions for He could be ascribed to elastic scattering and thermodynamic processes. The diffusion of ions in He resulted in a longer delay before the instrument registered its maximal signal. Ions with different masses were observed to have the same kinetic energies in He, which was confirmed using the SIMION software, while ion movement was hydrodynamically controlled in Ar. The velocities of singly and doubly charged ions were also studied, and doubly charged ions showed much higher kinetic energy because of their frontal location in the plasma expansion.     

Application of argon as the internal standard method in glow discharge mass spectrometry

Using (78)Ar(2)(+) as the internal standard (argon internal standard) in glow discharge mass spectrometry (GDMS) was investigated in detail. After comparing ion intensities and interferences, i.e. of argon ions, bi-atom argon ions and tri-atom argon ions, the (78)Ar(2)(+) was selected as the internal standard in the analysis. Mass spectral behavior of the argon internal standard affected by glow discharge current and voltage were studied. The ion intensity relationship between the argon internal standard and the matrix internal standard showed that the argon internal standard and the matrix internal standard have the same corrective effect on sample analysis. The experiment proved that the effects of the difference in analysis samples and the fluctuation of discharge conditions for analytical results were efficiently reduced if the argon internal standard was used. Moreover, the argon internal standard is similar to the matrix internal standard in correcting analytical results and both give satisfactory results. Elemental content in samples can be accurately determined by using the argon internal standard when the matrix content is unknown with good results.     

A molecular dynamics simulation of rebound,capture and diffusion in collisions at thermal energies between a rare gas atom and an argon cluster (n=125)

Molecular dynamics calculations have been performed to simulate the low energy collision (0.2 eV) of a rare gas atom (He, Ar, Xe) with a cluster of 125 argon atoms. Depending on its relative mass to argon, the projectile is either deflected (He) or captured (Ar, Xe) by the argon cluster. We have determined the deflection function of the He projectile that is scattered, and for Xe we have determined wether it stays near the surface of the cluster or migrates inside. These results have been discussed in the light of very simple models.     

Negative ion mass spectrometry: The generation of high concentrations of low energy molecular negative ions at high source pressures

The effect of the addition of argon and other gases upon the intensities of negative ion species formed in an electron impact source has been investigated. The negative ion current generated for a series of aromatic compounds has been investigated as a function both of sample and argon pressure in the ion source of a ZAB-2F mass spectrometer. For all compounds studied, a striking enhancement of molecular negative ion current occurred on increasing either the presure of the sample or of argor. The results are consistent with thermalization of the 50 eV electrons by collisions with neutral molecules in the high pressure ion source and collisional stabilization of the negative ions initially formed. Analytical applications of the technique are discussed.     

Spectroscopic study of a magnetically rotating arc between opper electrodes in contaminated argon

The effects of N₂ and CO contaminants in atmospheric-pressure argon on an arc rotating between two concentric copper electrodes has been studied using optical spectroscopy of copper lines. The axial temperature of the magnetically driven arc in Ar + %N₂ was determined to be around 10,000 K for arc currents of SO to 200 A. The diffusion process of the copper vapor from the cathode was also studied. A copper density maximum 1 mm from the cathode along the arc column was found in Ar + %N₂. Removal of the contaminated cathode surface layers by the arc when contaminant injection in the plasma gas was stopped was found to be a slow process with a time scale depending on the type of the gas contaminant. The presence of gas contaminant in the electrode material controls the cathode erosion mechanism and the overall arc behavior in the transition between a contaminated to a pure argon arc.     

Characterization of direct-current atmospheric-pressure discharges useful for ambient desorption/ionization mass spectrometry

Two relatively new ambient ionization sources, direct analysis in real time (DART) and the flowing atmospheric-pressure afterglow (FAPA), use direct current, atmospheric-pressure discharges to produce reagent ions for the direct ionization of a sample. Although at a first glance these two sources appear similar, a fundamental study reveals otherwise. Specifically, DART was found to operate with a corona-to-glow transition (C-G) discharge whereas the FAPA was found to operate with a glow-to-arc transition (G-A) discharge. The characteristics of both discharges were evaluated on the basis of four factors: reagent-ion production, response to a model analyte (ferrocene), infrared (IR) thermography of the gas used for desorption and ionization, and spatial emission characteristics. The G-A discharge produced a greater abundance and a wider variety of reagent ions than the C-G discharge. In addition, the discharges yielded different adducts and signal strengths for ferrocene. It was also found that the gas exiting the discharge chamber reached a maximum of 235 °C and 55 °C for the G-A and C-G discharges, respectively. Finally, spatially resolved emission maps of both discharges showed clear differences for N₂⁺ and O(I). These findings demonstrate that the discharges used by FAPA and DART are fundamentally different and should have different optimal applications for ambient desorption/ionization mass spectrometry (ADI-MS).     

Numerical analysis of the behavior of hydrogen added into a free-burning arc

The objective of the present work is to investigate the behavior of hydrogen in an atmospheric-pressure free-burning argon are when a small amount of hydrogen is added into the arc. A two-dimensional model calculation is carried out under the assumption that the ionization reaction of argon is in equilibrium and the reactions among hydrogen molecules, atoms, ions, and electrons are not necessarily in equilibrium. This calculation gives the following conclusion. The hydrogen mass fraction of 0.001 is too small to affect the flow and temperature fields markedly, and the concentration ratios among the hydrogen species are in equilibrium in the greater part of the arc region except for same parts with a steep temperature gradient. The hydrogen mass Junction, however, is not uniform in the me and, especially in the high-temperature region near the cathodes, over three dynes mass fraction of the hydrogen accumulates and flows downstream to cause a high flux of hydrogen atom toward the anode. This phenomena can be explained by the large difference between the diffusivity of hydrogen atom and that of hydrogen ion in argon ion.     

Elimination of the concentration dependence in mass isotopomer abundance mass spectrometry of methyl palmitate using metastable atom bombardment

An important problem in mass isotopomer abundance mass spectrometry (MIAMS) is the dependence of measured mass isotopomer abundances on sample concentration. We have evaluated the role of ionization energy on mass isotopomer abundance ratios of methyl palmitate as a function of sample concentration. Ionization energy was varied using electron impact ionization (EI) and metastable atom bombardment (MAB). The latter generates a beam of metastable species capable of ionizing analyte molecules by Penning ionization. We observed that ionization of methyl palmitate by EI (70 eV) showed the greatest molecular ion fragmentation and also showed the greatest dependence of relative isotopomer abundance ratios on sample concentration. Ionization using the 3P2 and 3P0 states of metastable krypton (9.92 and 10.56 eV, respectively) resulted in almost no molecular ion fragmentation, and the isotopomer abundances quantified were essentially independent of sample concentration. Ionization using the 3P2 and 3P0 states of metastable argon (11.55 and 11.72 eV, respectively) showed molecular ion fragmentation intermediate between that of EI and MAB(Kr) and showed an isotopomer concentration dependence which was less severe than that observed with EI but more severe than that observed with MAB(Kr). The observed decrease in the dependence of isotopomer abundance on sample concentration with a decrease in molecular ion fragmentation is consistent with the hypothesis that proton transfer from a fragment cation to a neutral molecule is the gas phase reaction mechanism responsible for the concentration dependence. Alternative explanations, e.g., hydrogen abstraction from a neutral molecule to a molecular cation, is not supported by these results. Moreover, the MAB ionization technique shows potential for eliminating one source of error in MIAMS measurements of methyl palmitate, in particular, and of fatty acids methyl esters, in general.     

A comparison of electron ionization mass spectra obtained at 70 eV,low electron energies,and with cold EI and their NIST library identification probabilities

Electron ionization (EI) mass spectra of 46 compounds from several different compound classes were measured. Their molecular ion abundances were compared as obtained with 70‐eV EI, with low eV EI (such as 14 eV), and with EI mass spectra of vibrationally cold molecules in supersonic molecular beams (Cold EI). We further compared these mass spectra in their National Institute of Standards and Technology (NIST) library identification probabilities. We found that

1. Low eV EI is not a soft ionization method, and it has little or no influence on the molecular ion relative abundances for large molecules and those with weak or no molecular ions.
2. Low eV EI for compounds with abundant or dominant molecular ions in their 70 eV mass spectra results in the reduction of low mass fragment ions abundances thereby reducing their NIST library identification probabilities thus rarely justifies its use in real‐world applications.
3. Cold EI significantly enhances the relative abundance of the molecular ions particularly for large compounds; yet, it retains the low mass fragment ions; hence, Cold EI mass spectra can be effectively identified by the NIST library.
4. Different standard EI ion sources provide different 70 eV EI mass spectra. Among the Agilent technologies ion sources, the “Extractor” exhibits relatively abundant molecular ions compared with the “Inert” ion source, while the “High efficiency source” (HES) provides mass spectra with depleted molecular ions compared with the “Inert” ion source or NIST library mass spectra.

These conclusions are demonstrated and supported by experimental data in nine figures and two tables.     

Fragmentation spectroscopy of heterogeneous clusters

Photoionisation experiments were performed with heterogeneous Ar-Xe-clusters produced by supersonic expansion of argon gas with small quantities of xenon added to it. A threshold-electron photoionisation (TEPICO) technique was used to obtain time of flight cluster mass spectra. These mass spectra show particularly strong intensities for Ar₁₂Xe⁺ and Ar₁₈Xe⁺ which are attributed to the extraordinary stabilities of these cluster ions. Maxima in the ionic size distribution around Ar₇Xe⁺ are related to a particular abundance ofneutral Ar₁₂Xe which is fragmented after ionization. These stabilities are explained in terms of geometries consisting of a central Xe atom or ion surrounded by shells of Ar atoms. Filled shells exhibit particular strong bonding because these exhibit the largest number of atom-atom bonds. This conclusion is supported by simple theoretical calculations. The ionization process is discussed in terms of two direct and one indirect ionization channels the latter one proceeding via an intermediate electronic excitation of the Ar component in the neutral cluster.     

Chemical ionization and electron impact mass spectrometry of some organophosphonate compounds

The application of gas chromatography chemical ionization mass spectrometry to the determination of a variety of alkyl alkylphosphonates, phosphonofluoridates, phosphonothiolates and an amidophosphorocyanidate is described. Comparison is made between the electron ionization and chemical ionization mass spectrometry of these compounds. Chemical ionization mass spectrometry is shown to enhance the capability for identification, especially when a limited sample is available. Results indicate that methane is highly useful for obtaining protonated molecular ions and association ions (formed by the transfer of a reactant ion to a sample molecule) as well as meaningful fragment ions. Ionizing ethylene and isobutane gives protonated molecular ions as base peaks for all of the compounds studied, including those where a lower abundance of the [MH]₊ ion is found via methane chemical ionization mass spectrometry. Ethylene is superior to isobutane on the basis of its effectiveness for serving as both a carrier and a reagent gas and gives better sensitivity. Although not an intrinsic part of this present study, analytical sensitivities in the subnanogram range were found.