Search

Tandem mass spectrometry based on ion-molecule reactions has emerged as a powerful tool for structural elucidation of ionized analytes. However, most currently used reagents were designed to react with protonated analytes, making them suboptimal for acidic analytes that are preferentially detected in negative ion mode. In this work we demonstrate that the phenoxide, carboxylate, and phosphate functionalities can be identified in deprotonated molecules by use of a combination of two reagents, diethylmethoxyborane (DEMB) and water. A novel reagent introduction setup that allowed DEMB and water to be separately introduced into the ion trap region of the mass spectrometer was developed to facilitate fundamental studies of this reaction. A new reagent, diethylhydroxyborane (DEHB), was generated inside the ion trap by hydrolysis of DEMB on introduction of water. Most carboxylates and phenoxides formed a DEHB adduct, followed by addition of one water molecule and subsequent ethane elimination (DEHB adduct +HO − CHCH) as the major product ion. Phenoxides with a hydroxy group adjacent to the deprotonation site and phosphates formed a DEHB adduct, followed by ethane elimination (DEHB adduct − CHCH). Deprotonated molecules with strong intramolecular hydrogen bonds or without the aforementioned functionalities, including sulfates, were unreactive toward DEHB/HO. Reaction mechanisms were explored via isotope labeling experiments and quantum chemical calculations. The mass spectrometry method allowed the differentiation of phenoxide-, carboxylate-, phosphate-, and sulfate-containing analytes. Finally, it was successfully coupled with high-performance liquid chromatography for the analysis of a mixture containing hymecromone, a biliary spasm drug, and its three possible metabolites. [ABSTRACT FROM AUTHOR]

In the vicinity of Europa, Galileo observed bursty Alfvén-cyclotron wave power at the gyrofrequencies of a number of species including K+, O [ABSTRACT FROM AUTHOR]

Resonant electron attachment by orotic acid molecules (6-COOH-uracil) are studied in the energy range of 0-14 eV via negative ion mass spectrometry. Molecular ions, whose lifetimes relative to electron autodetachment are found to be ~300 μs are recorded in the region of thermal electron energies; they form in the valence state through a vibration-excited resonance mechanism. Unlike unsubstituted uracil, most dissociative processes occur in the low-energy region of <4 eV and are due to carboxylic anions. An absolute cross section of 2.4 × 10 cm is found for the most intense fragment ions [M-H] at an output energy of 1.33 eV. The kinetics of decarboxylation is considered for these ions. This could be a model reaction for the last stage of uridine monophosphate biosynthesis. [ABSTRACT FROM AUTHOR]

The Ion Laser InterAction Setup (ILIAS) project at the University of Vienna aims at the exploration of negative ion beam filtering by selective laser photodetachment for applications in accelerator mass spectrometry (AMS). A gas-filled radio frequency quadrupole (RFQ) is used to decelerate and cool negative atomic and molecular ion beams with intensities of up to several hundred nA, and overlap them collinearly with a continuous wave (cw) laser beam. Ion-laser interaction times ranging from 500 μs to several ms allow for highly efficient, selective photodetachment depletion of disturbing ion species within these beams. The elemental selectivity of this technique is based on the differences in electron affinities, and therefore does not depend on relative differences in atomic numbers. It may therefore provide sufficient isobar suppression for new trace isotopes, which are not accessible with existing AMS techniques. The ILIAS RFQ cooler was characterized at a purpose-built test bench with respect to ion beam transmission, ion cooling capabilities and ion residence times as a function of injected ion current to assess its suitability for future AMS use. A 63 Cu − test beam of 600 nA was photodetached with more than 99.999% efficiency with a 532 nm laser at 10.8 W power. At the same time, ions of interest having electron affinities higher than the photon energy passed the cooler unaffected. Total ion losses were thus found to be below 50% of the sputter source output. Finally, first photodetachment experiments in connection with 26 Al detection demonstrated selective isobar suppression of MgO − vs. AlO − by more than 4 orders of magnitude. Currently, the RFQ cooler is moved to a new injector beamline at the Vienna Environmental Research Accelerator (VERA) for first applications of this novel technique at a state-of-the-art AMS facility. [ABSTRACT FROM AUTHOR]

A comparative investigation into the chemical reactions of a series of fluorinated fullerenes (C 60 F 18 , C 60 F 36 and C 60 F 48 ) with a variety of activated metal surfaces is reported. New ways of generating intense beams of metal fluoride anions are demonstrated: either in reactions of fluorinated fullerene vapours with hot W and Mo metal surfaces in a plasma ion source or by laser desorption/ionisation (LDI) of solid fluorinated fullerenes from various metal substrates (Al, Fe, Cu, Pt, W). In both cases, the resulting metal fluorides and their anions are formed in the highest oxidation state, yielding molybdenum and tungsten hexafluoride anions (plasma ion source), aluminium and iron tetrafluoride anions, and copper trifluoride anions (LDI). No reactions were observed with Pt and W in LDI. The reactivity of the metals towards fluorination correlates with their positions in the metal activity series. Relative yields of bare metal cations are dictated by their ionisation energy. The yield of metal fluoride anions is strongly dependent on the fluorine content of the fluorofullerenes. [ABSTRACT FROM AUTHOR]

The frequency domain dielectric response method has been one of the most effective approaches for condition assessment of an electrical insulation system. The low‐frequency part is more effective for diagnosing the moisture content and aging status of oil‐paper insulation. To facilitate the study of the low‐frequency dielectric spectrum of oil‐paper insulation, a model applicable to the low‐frequency dielectric response of insulation oil is proposed in this study, which is based on the ionic motion of insulation oil. The creation of charge carriers under field test conditions mainly derives from the dissociation of ionic pairs. During testing, ionic motion of insulation oil is jointly affected by thermal diffusion and the electric field; moreover, dissociation and recombination of negative and positive ions also occur. Therefore, the above factors were all considered in the modelling process. The applicability of the model is verified against measured results. For further interpreting the proposed model, the characteristics of the ionic concentration distribution, the relation between ionic distribution and dielectric properties, and the application of the proposed model are analysed. [ABSTRACT FROM AUTHOR]

This contribution describes the design of a movable Langmuir probe system to be permanently installed in the SPIDER negative ion source. This diagnostic aims at measuring the axial profiles of plasma density, electron temperature and floating potential in both the driver and the expansion region, with a view to further investigate the positive ion dynamics. Furthermore, a deeper understanding of the plasma formation mechanism and of the RF coupling can be provided, e,g. via the estimation of the Electron Energy Distribution Function (EEDF) inside the driver. Thermal analyses were performed to define both the allowable duration of the probe exposure to the plasma and the extent of the voltage sweep. The maximum exposure time for the probe shaft is 10 s, thus a fast manipulation system is included in the design. The integration in the SPIDER source is described, considering all the limitations due to the space availability, the presence of the RF generators and the vacuum-compatibility requirements. To comply with all the constraints, several solutions are proposed for the probe head design. • Negative ion sources are necessary for high energy neutral beam injectors. • The beam optics are strongly related to the source plasma parameters. • It is necessary to investigate the source plasma properties with diagnostics. • A permanently installed movable Langmuir probe is designed for the SPIDER source. • Several technical aspects (vacuum-compatibility, RF noise) need to be addressed. [ABSTRACT FROM AUTHOR]

In sputter-type negative ion sources, the negative ion currents and ionization efficiencies are very dependent upon the creation of a sputter crater and formation of an intense plasma glow. This effect has many similarities with the well-known phenomena of hollow cathode discharges (HCDs). This paper discusses the phenomenological model related to conventional HCDs, including modes with injection of external energetic particles. We propose that HCDs play a major role in sputter-type negative ion sources. In this study, we evaluate the phenomenology of a discharge with a hollow cathode and derive an analytical formula that defines the neutral particle density inside the cathode cavity and substantiates how the classic HCD occurs in sputter-type negative ion sources. The cathode pit geometry was revealed by optical microscopy. Volt–ampere characteristics were investigated in order to compare it to typical discharges with hollow cathodes. In sputter-type negative ion sources, known as SNICS, discharge characteristics and observed light glow inside the cathode pit after its formation were very similar to data published on HCDs. The HCD phenomenon explains how the cathode current increases by orders of magnitude after creation of the cathode pit. The HCD effect in SNICS and similar sputter sources compliments existing mechanisms of negative ion production, especially ion pair production close to the cathode surface due to low energy ionization based on the collision–radiation model. The wealth of information accumulated over the last century on HCDs can be used to describe and explain the phenomenology of physics and operation of sputter negative ion sources. • Phenomenology of discharge with hollow cathode has been associated with Caesium sputter negative ion source SNICS. • Understanding processes in the SNICS is imperative to continuous development of this device and improving its efficiency. • The wealth of information on HCD can be used to explain the phenomenology of physics of sputter negative ion sources. [ABSTRACT FROM AUTHOR]

In this work we present swarm data obtained for F- ions in atomic and molecular gases necessary to form the global models for the complex collisional plasmas. We also present the new results for the simple scattering cross section set and proposed transport coefficients for F- ions in BF3 that can be used in such models. Nanbu’s theory based on thermodynamic threshold energies and separating elastic and reactive collisions is used to calculate cross sections for binary collisions of ions with atoms and molecules. For the cases in which the measured transport coefficients were available Momentum Transfer theory (MTT) was applied in order to unfold the cross sections from the measured transport data. Direct Monte Carlo method is applied to obtain swarm parameters at the temperature of T=300 K.

A study to determine the conceptual design of a 13 MeV proton cyclotron for PET (Positron Emission Tomography) facility has been carried out. Based on studies on reactions of PET radioisotopes production, reaction cross-sections and some design references, a design of the proton cyclotron is proposed. The design criteria for the main components are decided using empirical and semitheoretical methods, as well as by referring to data regarding cyclotrons for PET production. The empirical method was carried out by using some data from operational experiences of BATAN cyclotron at Serpong, while the semitheoretical method was carried out by using the commonly used equations of cyclotron basic theory. The general layout of components and the main components, namely the ion source, the RF dees, the magnet, and the extractor are discussed. Based on the calculations and on the data used, the cyclotron is designed as a negative ion acceleration cyclotron with internal ion source. The designated proton energy and beam currents are 13 MeV and 50 µA. Its magnetic field is in the relativistic mode with sectors on the pole. The magnetic field intensity at the extraction radius is 12.745 kG and in the innermost radius is 12.571 kG. The magnetic poles consist of four sectors to make adequate space for components placement such as dees, ion source, extractor and beam probe. The dee angle is 430. The dee operates at 78 MHz on the fourth harmonic. A multifoil extractor is chosen to obtain an efficient operation

An electrostatic apparatus was constructed to capture tobacco sidestream smoke. This apparatus consisted of a perforated polypropylene plate with metal spikes and a grounded metal net arrayed in parallel at a defined interval. Spikes were negatively charged to positively polarize the net and an electric field was formed between the opposite charges of the spike tips and the grounded net. Discharge from the spike tips occurred, which depended on the pole distance and the voltage applied to the spikes. At lower voltages (

A new experimental system was recently developed to measure the mobility of both positive and negative ions: the Dual-Polarity Ion Drift Chamber (DP-IDC). This system is intended to better understand the transport properties of ions in gases relevant for the performance of large volume gaseous detectors like the Negative Ion Time Projection Chambers (NITPCs). In this work, we present a description of the experimental setup and technique used, and the initial studies carried out in Xe–S F 6 mixtures, whose interest has attracted attention as a possible alternative in searches for the neutrinoless double-beta decay. [ABSTRACT FROM AUTHOR]

We have formed the Al(I)-containing molecule, benzophenone-aluminum, i.e., Ph 2 COAl, and studied it by conducting density functional theory calculations on both its neutral and anionic forms and by measuring the photoelectron spectrum of its anion. Our calculations identified two nearly iso-energetic anion isomers, (Ph 2 COAl) − , the vertical detachment energies (VDE) of which are in excellent agreement with our photoelectron spectrum. Natural population analysis (NPA) of Ph 2 COAl found the Al moiety to be positively charged by +0.81 e , indicating a strongly ionic bond between Al and Ph 2 CO, i.e., Ph 2 CO − Al + . [ABSTRACT FROM AUTHOR]

The paper describes a new phenomenon of the generation of the double electrical layer above the cathode spot surface. The neutralization of this layer leads to the reverse current of free electrons, generated due to negative ions ionization. The negatively charged flame of the cathode spot periodically ignites and attenuates, so the duration of the cathode spot existence is defined by this oscillating process. The reverse motion of the cathode spot in the longitudinal magnetic field takes place owing to the generation of the reverse high-power neutralization current of the double electrical layer by the electrons appearing during the negative ions ionization in the cathode flame. [ABSTRACT FROM AUTHOR]

Using a static sector magnetic mass spectrometer MI-1201B, modified to record negative ions for resonant electron capture by molecules, the ion extraction time from the ionization chamber combined with this apparatus was measured up to several hundred microseconds. It was shown that the values obtained are anomalously great and they arise from the fact that part of the formed in the ionization chamber ions are adsorbed onto the chamber's surface. Those of them that were produced initially in the gas phase, namely the transient negative ions, with a finite lifetime (∼1 μs and greater), transform themselves, on the surface, into ‘infinitely living’ (stable) ions. As a result, the contribution of the stable ions to the total ion beam falsifies the ion's lifetime measurements performed with this instrument. [ABSTRACT FROM AUTHOR]

The processes of resonance low-energy free electron attachment to methyl esters of some sulfur-containing amino acids were studied. The long-lived molecular negative ions of cystine dimethyl ester formed in the valence state via the Feshbach nuclear excited resonance mechanism were detected by mass spectrometry. The reactions of disulfide bond dissociation were identified in an electron energy range of 0-1 eV. They can be considered as model reactions regarding processes of peptide decomposition due to the resonance interaction with low-energy electrons. Predissociation of short-lived molecular ions of cysteine methyl ester formed by capture of electrons with energies of ~1.6 eV is accompanied by the intra-ionic transfer of negative charge from the carbonyl group to the sulfur atom leading to the elimination from the latter of hydrogen atom. [ABSTRACT FROM AUTHOR]

This review presents some of the recent advancements in our understanding of comets facilitated by laboratory studies, need for new laboratory simulations, and predictions for future explorations. With the spacecraft Rosetta at the comet 67P/Churyumov-Gerasimenko, a large volume of science data is expected to follow early results that have been published recently. The most surprising of them being hard ice shell that bounced the lander Philae a couple of times before settling on the comet. Long evaded molecular nitrogen has now been detected in the comet 67P/CG. The observed density of $470~\mbox{kg}\,\mbox{m}^{- 3}$ is in line with other comet observations, whereas the nature and composition of hydrocarbons detected on the surface are still a puzzle. Observation of D/H ratio that deviates significantly from Earth's water D/H ratio brings back to the table the long-standing question whether or not water on Earth was delivered by comet impacts. Our review summarizes some of the critical laboratory work that helps improve our understanding of cometary interior (whether amorphous or crystalline or containing clathrates), cometary surface (rich of complex organics), cometary coma and tail (D/H ratio, negative ions, and photoluminescence). Outstanding questions are also discussed. [ABSTRACT FROM AUTHOR]

Plasma parameter measurements for negative hydrogen (H ^− ) ion sources have been playing an important role in clarifying fundamental physics related to negative ion production and destruction processes. Measured data of beam properties, such as H ^− ion current density with the co-extracted electron current and the emittance, were correlated to local concentration of charged particles and temperature often characterized by Langmuir probes and optical emission spectrometry. Langmuir probes coupled to pulse lasers quantified local H ^− ion densities from early days of H ^− ion source development, while the cavity ring down photodetachment method removed Langmuir probes from contemporary large-size high power density ion sources. Technological progress has made source plasma diagnostics possible during beam extraction, which has thrown light on the transport of H ^− ions during the application of the extraction electric field. The advancement of plasma diagnostics for high intensity H ^− ion sources are summarized in this report together with recent results from the research and development negative ion source being operated for collaborative research programs at National Institute for Fusion Science.

Negative ion sources for fusion are high densities plasma sources in large discharge volumes. There are many challenges in the modeling of these sources, due to numerical constraints associated with the high plasma density, to the coupling between plasma and neutral transport and chemistry, the presence of a magnetic filter, and the extraction of negative ions. In this paper we present recent results concerning these different aspects. Emphasis is put on the modeling approach and on the methods and approximations. The models are not fully predictive and not complete as would be engineering codes but they are used to identify the basic principles and to better understand the physics of the negative ion sources.

The heating neutral beam injectors (HNBs) of ITER are designed to deliver 16.7 MW of 1 MeV D ^0 or 0.87 MeV H ^0 to the ITER plasma for up to 3600 s. They will be the most powerful neutral beam (NB) injectors ever, delivering higher energy NBs to the plasma in a tokamak for longer than any previous systems have done. The design of the HNBs is based on the acceleration and neutralisation of negative ions as the efficiency of conversion of accelerated positive ions is so low at the required energy that a realistic design is not possible, whereas the neutralisation of H ^− and D ^− remains acceptable (≈56%). The design of a long pulse negative ion based injector is inherently more complicated than that of short pulse positive ion based injectors because: • negative ions are harder to create so that they can be extracted and accelerated from the ion source; • electrons can be co-extracted from the ion source along with the negative ions, and their acceleration must be minimised to maintain an acceptable overall accelerator efficiency; • negative ions are easily lost by collisions with the background gas in the accelerator; • electrons created in the extractor and accelerator can impinge on the extraction and acceleration grids, leading to high power loads on the grids; • positive ions are created in the accelerator by ionisation of the background gas by the accelerated negative ions and the positive ions are back-accelerated into the ion source creating a massive power load to the ion source; • electrons that are co-accelerated with the negative ions can exit the accelerator and deposit power on various downstream beamline components. The design of the ITER HNBs is further complicated because ITER is a nuclear installation which will generate very large fluxes of neutrons and gamma rays. Consequently all the injector components have to survive in that harsh environment. Additionally the beamline components and the NB cell, where the beams are housed, will be activated and all maintenance will have to be performed remotely. This paper describes the design of the HNB injectors, but not the associated power supplies, cooling system, cryogenic system etc, or the high voltage bushing which separates the vacuum of the beamline from the high pressure SF _6 of the high voltage (1 MV) transmission line, through which the power, gas and cooling water are supplied to the beam source. Also the magnetic field reduction system is not described.

[Display omitted] • The doubly excited 1Po resonance states in H−and Ps− are studied. • Variational methods and correlated exponential wavefunctions are used. • Resonance positions, widths, autoionization decay rates are calculated. • Oscillator strengths (OS) and radiative decay rates are reported. • The ratios of OS between the Feshbach and shape resonances are presented. The autoionization decay (AD) and radiative decay (RD) for doubly excited 1Po resonance states in H− and Ps− are studied using correlated exponential wavefunctions based on the variational methods. To trace the resonance poles from Ps− to H−, the nuclear mass is varied from one unit to infinitely heavy. Resonance positions, widths related to AD rates, oscillator strengths, the ratios of oscillator strengths between the Feshbach and shape resonances (FSR), RD rates for the lowest two FSR in the 1Po spectrum, are reported. Few results are new, and others are comparable with the available theoretical and experimental data. [ABSTRACT FROM AUTHOR]

Field desorption (FD) traditionally is an ionization technique in mass spectrometry (MS) that is performed in high vacuum. So far only two studies have explored FD at atmospheric pressure or even superatmospheric pressure, respectively. This work pursues ion desorption from 13-µm activated tungsten emitters at atmospheric pressure. The emitters are positioned in front of the atmospheric pressure interface of a Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer and the entrance electrode of the interface is set to 3-5 kV with respect to the emitter. Under these conditions positive, and for the first time, negative ion desorption is achieved. In either polarity, atmospheric pressure field desorption (APFD) is robust and spectra are reproducible. Both singly charged positive and negative ions formed by these processes are characterized by accurate mass-based formula assignments and in part by tandem mass spectrometry. The compounds analyzed include the ionic liquids trihexyl(tetradecyl) phosphonium tris(pentafluoroethyl) trifluorophosphate) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, the acidic compounds perfluorononanoic acid and polyethylene glycol diacid, as well as two amino-terminated polypropylene glycols. Some surface mobility on the emitter is prerequisite for ion desorption to occur. While ionic liquids inherently provide this mobility, the desorption of ions from solid analytes requires the assistance of a liquid matrix, e.g. glycerol.

We explore the possibility that the fast and exotic negative ions in superfluid helium are electrons bound to quantized vortex structures, the simplest being a ring. In the states we consider, the electron energy is only slightly below the conduction band minimum of bulk helium. To support our proposal, we present two calculations. In the first, we show that the electron pressure on the vortex core is insufficient to cavitate the helium and form an electron bubble. In the second, we estimate the equilibrium radius of the vortex ring that would bind an electron and find it is much smaller than the electron bubble, about 7 Å. The many exotic ions reported in experiments might be bound states of an electron with more complex vortex structures. [ABSTRACT FROM AUTHOR]

Copyright of Journal of Nano- & Electronic Physics is the property of Sumy State University and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

There are number of ways in which weak electrification can affect the microphysics of clouds, with consequences for cloud lifetime, radiative properties, and precipitation efficiency. Kauffman [2011] suggested ions produced by direct current generators will add to and enhance the catalysing effects that cosmic ray ions are now known to produce in among other things, lowering nucleation barriers, stimulating charged particle growth and stability and increasing the scavenging rate in clouds. Thus to electrify the atmosphere ions can be generated artificially in abundance along with large electric field. Ions can be generated by the corona effect using Atmospheric electrifiers (a device used to generate negative ions) which makes use of corona discharge phenomenon to charge the air particles. Exact assessment of electric field and charge density distributions and the flow dynamics inside the electrifiers is essential to understand the particle behaviour inside the electrifiers. In this paper, a novel model of governing equations to evaluate the space charge density, electric field intensity and velocity of ionized airflow is suggested as a function of applied voltage. The Poisson and charge conservation equations are derived and hence can be used to estimate the electric field and charge density distributions. Navier stokes equation can be used to get the velocity of ionized airflow because of electric force on the air. Simulation is carried out to validate the proposed model and verify that velocity is function of input voltage and is proportional to it. [ABSTRACT FROM AUTHOR]

In this study we have examined the formation of ions from hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) sample evaporated at 473 K in reactions with reactant ions (RI) produced in negative corona discharge (CD). The ions have been analysed and detected by ion mobility spectrometry coupled to orthogonal acceleration time of flight spectrometer (IMS-oaTOF). The chemical ionisation was carried out by O, O (HO), NO, NO and NO (HO) RI formed in CD operated in zero air in the reverse gas flow mode at elevated temperatures 438 K and by Cl(HO) ( n = 0,1,2) at 332 K. In case of 332 K, the RI were prepared by admixture of carbon tetrachloride (CCl - dopant gas) in order to enhance sensitivity of RDX. [ABSTRACT FROM AUTHOR]

In the present paper the processes of resonant electron attachment by trifluoroacetic acid molecules (CF 3 COOH) and its deuterated analog (CF 3 COOD) leading to formation of fragment negative ions have been investigated by negative ion mass spectrometry. Inverse or small direct isotope effect was detected for majority of negative ions. It is expressed both in difference between cross-section of ion formation, and in resonance peak displacement over energy scale for isotopically substituted ions from CF 3 COOH and CF 3 COOD. Isotope effect of maximal magnitude σ (H) / σ (D) ≈ 19 was registered for (M−H/D) − ions at electron energy 0.73 eV, and formation of these ions was explained by the mechanism of tunneling predissociation. [ABSTRACT FROM AUTHOR]

A non-linear computational modelling of ions from the ground station for electrifying the atmosphere to make feasibility study of artificial rainfall system is proposed and analyzed. The model considers generation of intermediate ions and ionized airflow velocity. The governing electro hydrodynamic (EHD) equations of the model shows that the space charge density, electric field intensity and velocity of the ionized airflow are function of high input voltage applied to generate the ions. The number of ions generated and their velocity is proportional to the applied ion generator voltage. These artificial ions will be introduced in the atmosphere which will act in a similar manner as cosmic rays. These ions will ionize the aerosols and catalyze nucleation processes and thus electrify the atmosphere which will form cloud droplets to get artificial rain. The mathematical model to study the feasibility of artificial rainfall is also validated under favourable conditions. [ABSTRACT FROM AUTHOR]