Multiply Charged Ions Research Articles

A modified magnetic bottle electron spectrometer for the detection of multiply charged ions in coincidence with all correlated electrons: decay pathways to Xe3+ above xenon-4d ionization threshold

New magnet design of a magnetic bottle electron spectrometer allowing the detection of multiply charged ions in coincidence with n electrons. Electrons spectra obtained without and with filtering by coincidence with Xen+ ions.

THEORETICAL STUDYING SPECTRAL CHARACTERISTICS OF Zn-LIKE IONS ON THE BASIS OF RELATIVISTIC MANY-BODY PERTURBATION THEORY

A theoretical study of the spectroscopic characteristics of Zn-like multiply charged ions is carried out within the framework of the relativistic many-body perturbation theory. The optimized Dirac-Kohn-Shem approximation was chosen as the zero approximation of the relativistic perturbation theory. Optimization has been fulfilled by means of introduction of the parameters to the Kohn-Sham exchange and correlation potentials and further minimization of the gauge-non-invariant contributions into radiation width of atomic levels with using relativistic orbital set, generated by the corresponding zeroth approximation Hamiltonian.

Combined electrostatic analyzer—Wien filter probe for characterization of species distributions in Hall thrusters

We present a combined electrostatic and magnetostatic plasma diagnostic tool used to measure current fractions of ion species in a Hall-effect thruster plume. Hall thrusters produce thrust by accelerating singly and multiply charged ions to high velocity. Singly charged ions fall through potential differences from their point of creation to the location of measurement, which varies as a function of time and position resulting in a relatively wide distribution of energy. This process is further complicated by both direct and multi-step creation of multiply charged ions and by ion-neutral collisions. The result is that Wien velocity filter (ExB) spectra typically have overlapping peaks. Analysis of these spectra requires assumptions about the velocity distribution function (VDF) that are hard to verify and can result in the incorrect species current distribution used to calculate thruster performance efficiencies. We present how adding an energy filter in line with an ExB probe can result in a more accurate measurement of the species current fraction while also providing information about the ion energy distribution of each species. The combined diagnostic was used to measure the species current distribution in a 1.5 kW Hall thruster operating on krypton. The diagnostic setup and data analysis of the probe measurements are presented and compared against results utilizing established VDF-fit and integration techniques applied to standard spectra measured by a standalone ExB probe.

Smart Readout of Nondestructive Image Sensors with Single Photon-Electron Sensitivity.

Image sensors with nondestructive charge readout provide single-photon or single-electron sensitivity, but at the cost of long readout times. We present a smart readout technique to allow the use of these sensors in visible light and other applications that require faster readout times. The method optimizes the readout noise and time by changing the number of times pixels are read out either statically, by defining an arbitrary number of regions of interest in the array, or dynamically, depending on the charge or energy of interest in the pixel. This technique is tested in a Skipper CCD showing that it is possible to obtain deep subelectron noise, and therefore, high resolution of quantized charge, while dynamically changing the readout noise of the sensor. These faster, low noise readout techniques show that the skipper CCD is a competitive technology even where other technologies such as electron multiplier charge coupled devices, silicon photo multipliers, etc. are currently used. This technique could allow skipper CCDs to benefit new astronomical instruments, quantum imaging, exoplanet search and study, and quantum metrology.

Experiment and theory elucidate the pathways for H3+formation in the ultrafast double ionization in methanol

Experiment and theory elucidate the pathways for H₃⁺formation in the ultrafast double ionization in methanol

Multiple ionization characteristics of hall thruster with large height–radius ratio and their effects

Increasing the specific impulse has become one of the main trends in the development of Hall thrusters and may be achieved by increasing the proportion of multiply charged ions in the plume. In this study, the multiple ionization characteristics of Hall thrusters with large height–radius ratios and their effects on the specific impulse and other performance parameters were examined via numerical simulations. The simulation results show that the proportion of multiply charged ions in a Hall thruster with a large height–radius ratio increases by 7.8 percentage points, compared with that of the traditional Hall thruster, and the multiply charged ions can obtain a higher average jet velocity under an accelerating voltage, thereby improving the specific impulse and thrust of the thruster. Further analyses show that a structure with a large height–radius ratio reduces the cooling effect of the channel wall on the electrons, and the increase in electron temperature effectively promotes the occurrence of the multiple ionization process. In addition, the smaller wall area and the larger magnetic field intensity in the near-wall region inhibit the electron near-wall conduction and prevent the potential negative effect of the increase in electron current caused by multiply charged ionization, which ensures a high level of efficiency. It was proved that multiple ionizations contribute positively to the specific impulse and efficiency of Hall thrusters with a large height–radius ratio. This serves as a reference for the high specific impulse design of Hall thrusters with large height–radius ratios and provides a new optimization perspective for improving the specific impulse of Hall thrusters.

Dielectronic recombination strengths and plasma rate coefficients of multiply charged ions

Context. Dielectronic recombination (DR) has been known as the dominant electron-ion recombination process in different astrophysical and laboratory plasmas, and that it determines the level population and ionization balance over a range of temperatures. Apart from a fundamental interest into the details of this process, DR plasma rate coefficients are frequently applied to estimate plasma densities and temperatures, but have been found to be notoriously difficult to calculate as they require good knowledge of the ionic resonances, which are embedded into the continuum of the next higher charges states. Aims. In this paper we explain and demonstrate how DR resonance strengths and plasma rate coefficients can be readily computed within the framework of the Jena Atomic Calculator (JAC). In contrast to other available codes, the JAC toolbox supports a much simpler handling and control of different approximations, shell structures and temperature regions, for which doubly excited resonances need to be taken into account. Methods. A multi-configuration Dirac–Hartree–Fock expansion of all atomic states is generated and applied in order to compute the transition rates (radiative and nonradiative) that contribute to the DR process. For the plasma rate coefficients, moreover, a cascade model has been developed that automatically determines and incorporates all doubly excited configurations of interest for the given plasma temperatures. Results. To demonstrate the quite flexible use of JAC, we discuss and compare the DR of initially fluorine-like Ni19+ ions with previous measurements and computations. Since it is based on Dirac’s equation, the JAC toolbox is suitable for most ions across the periodic table.

Bioanalytical method development and validation of highly selective and sensitive LC-MS/MS method for determination of teriparatide (parathyroid hormone fragment 1–34) in human serum through direct detection of intact teriparatide molecule

Teriparatide is a novel recombinant peptide fragment of the first 1–34 amino acids of human parathyroid recommended for treatment of osteoporosis. Therapeutic proteins and peptides are routinely estimated using ligand binding assay formats however LC-MS/MS technique which is routinely used in bioanalysis of small molecules has now gained importance in large molecule bioanalysis for the advantages it can offer over LBAs in terms of improved accuracy, selectivity and anti-body free method development. This paper presents a sensitive bioanalytical method for determination of teriparatide in human serum using ultra performance liquid chromatography aligned with tandem mass spectrometric detection. Teriparatide was isolated from human serum using solid phase extraction. The intact peptide was separated on a chromatograph and the multiply charged ion (+7) was detected using a mass spectrometer. The total run time was 4.0 min. The internal standard used was rat PTH 1–34 fragment. The mass transitions of m/z 589.3 > 656.3 for teriparatide and m/z 677.4 > 778.6 for internal standard were used for MS/MS detection. The sample extraction involved a solid phase extraction method followed by concentration of the eluent by evaporation and subsequent reconstitution. The non-specific binding effect caused by the adherence of the peptides/proteins to the vials/tube walls was significantly reduced by using BSA solution as blocking agent. The method has been validated over a linear range of 15.07–913.3 pg/mL with a correlation coefficient ≥ 0.99. The precision (%RSD) was 6.36 to 10.85 and accuracy was within 96.71% to 100.88%. A two-treatment, two-period, cross over study was conducted to establish bioequivalence between test and reference formulation (20 mcg/80 mL – solution for injection) and the method was successfully applied to quantify teriparatide in serum samples of this clinical study and about 1220 human serum samples were analyzed to determine teriparatide. This method is a promising anti-body free LC-MS/MS based methodology for estimation of teriparatide in human serum and may be applied as starting method for other such peptide molecules.

Effects of multiply charged ions on microturbulence-driven electron transport in partially magnetized plasmas

Nonlinear interaction between kinetic instabilities in partially magnetized plasmas in the presence of multiply charged ion streams is investigated using kinetic simulations. It was observed by Hara and Tsikata [Phys. Rev. E 102, 023202 (2020)] that the axial ion–ion two-stream instability due to singly and doubly charged ion streams, coupled with the azimuthal electron cyclotron drift instability (ECDI), enhances cross-field electron transport. In the present study, it is observed that the addition of triply charged ions (as a third ion species) contributes to damping of the excited modes, leading to a reduction in the cross-field electron transport. The net instability-driven electron transport is shown to be a function not only of the azimuthal modes, such as the ECDI, but of the multiple ion species that dictate the development of additional plasma waves. It is found that trapping of the higher ion charge states within the plasma waves results in broadening of the ion velocity distribution functions.

Identification of Multiply Charged Ions by Means of Detectors Based on Phosphate Glass

Identification of Multiply Charged Ions by Means of Detectors Based on Phosphate Glass

Intensity dependence of multiply charged atomic ions from argon clusters in moderate nanosecond laser fields.

We report the laser intensity dependence of multiply charged atomic ions (MCAIs) Arn+ with 2 ≤ n ≤ 8 from argon clusters in focused nanosecond laser fields at 532nm. The laser field, in the range of 1011-1012 W/cm2, is insufficient for optical field ionization but is adequate for multiphoton ionization. The MCAI sections of the mass spectra for clusters containing 3700 and 26 000 atoms are dominated by Arn+ with 7 ≤ n ≤ 9, extending to Ar14+. While the distributions of the MCAIs remain largely constant throughout the intensity range of the laser, the abundance of Ar+ relative to the abundances of the MCAIs increases dramatically with increasing laser intensity. Consequently, exponential fittings of the yields result in a larger exponent for Ar+ than for MCAIs, and the exponents of MCAIs with 2 ≤ n ≤ 8 are similar, with only slight variations for different charge states. The width of the arrival time and, hence, the corresponding kinetic energy of Ar+ also increases with increasing laser intensities, while the width of the arrival time of MCAIs remains constant throughout the range of measurements. These results call for more detailed theoretical investigations in this regime of laser-matter interactions.

Capillary ionic liquid electrospray: beam compositional analysis by orthogonal time-of-flight mass spectrometry

Orthogonal time-of-flight mass spectrometry has been used to characterize the kinetic energy and charged species distributions from an in vacuo electrospray ion source for four different ionic liquids at volumetric flow rates between 0.3 and 3.3 nanolitres per second. In all cases, the mass spectra revealed charged species consisting of singly charged and multiply charged ions as well as two broad, unresolved droplet distributions occurring in the 104 to 106 atomic mass unit per charge range. The mean jet velocity and mean jet breakup potential were established from analysis of the energy profile of the high mass-to-charge droplets. At the jet breakup point, we find the energy loss and the jet diameter flow rate dependence of the electrospray beam to be similar to that determined by Gamero-Castaño (Phys. Fluids, vol. 20, 2008, 032103; Phys. Rev. Fluids, vol. 8, 2021, 013701) for 1-ethyl-3-methylimidazolium bis(trifluromethylsulfonyl)imide at similar volumetric flow rates. Similar trends are observed for all four liquids over the flow regime. A jet instability analysis revealed that jet electrification and viscous effects drive the jet breakup from the case of an uncharged, inviscid jet; jet breakup occurs at droplet and jet radius ratios that deviate from 1.89. Using the analytically determined ratio and the beam profile, different species are modelled to reconstruct the mass spectra; primary droplets constitute only a fraction of the total species present. The populations of the species are discussed.

Mass Spectrometric and Bio-Computational Binding Strength Analysis of Multiply Charged RNAse S Gas-Phase Complexes Obtained by Electrospray Ionization from Varying In-Solution Equilibrium Conditions.

We investigated the influence of a solvent’s composition on the stability of desorbed and multiply charged RNAse S ions by analyzing the non-covalent complex’s gas-phase dissociation processes. RNAse S was dissolved in electrospray ionization-compatible buffers with either increasing organic co-solvent content or different pHs. The direct transition of all the ions and the evaporation of the solvent from all the in-solution components of RNAse S under the respective in-solution conditions by electrospray ionization was followed by a collision-induced dissociation of the surviving non-covalent RNAse S complex ions. Both types of changes of solvent conditions yielded in mass spectrometrically observable differences of the in-solution complexation equilibria. Through quantitative analysis of the dissociation products, i.e., from normalized ion abundances of RNAse S, S-protein, and S-peptide, the apparent kinetic and apparent thermodynamic gas-phase complex properties were deduced. From the experimental data, it is concluded that the stability of RNAse S in the gas phase is independent of its in-solution equilibrium but is sensitive to the complexes’ gas-phase charge states. Bio-computational in-silico studies showed that after desolvation and ionization by electrospray, the remaining binding forces kept the S-peptide and S-protein together in the gas phase predominantly by polar interactions, which indirectly stabilized the in-bulk solution predominating non-polar intermolecular interactions. As polar interactions are sensitive to in-solution protonation, bio-computational results provide an explanation of quantitative experimental data with single amino acid residue resolution.

Smallest Organic Tetracation in the Gas Phase: Stability of Multiply Charged Diiodoacetylene Produced in Intense Femtosecond Laser Fields.

Coulomb explosion imaging, which is the reconstruction of a molecular structure by measuring the three-dimensional momenta of atomic ions formed by a Coulomb explosion of multiply charged molecular cations (MMCs), has been utilized widely. In contrast, intact MMCs, whose properties and reactions are interesting from both fundamental and applied scientific perspectives, themselves have been little explored to date. This study demonstrates that the four-atom molecule diiodoacetylene (DIA) can survive as a long-lived species in the gas phase after the removal of four electrons in intense femtosecond laser fields. The electron configurations of the equilibrium structures of the electronic ground states calculated by the complete active space self-consistent field (CASSCF) method reveal the stability of multiply charged DIA. The dissociation energies are estimated to be 3.01, 3.59, 2.57, 1.82, and 1.61 eV for neutral, cation radical, dication, trication radical, and tetracation, respectively. A fairly deep potential well suggests that a DIA tetracation is metastable toward dissociation, whereas the repulsive potential of a pentacation radical confirms its absence in the mass spectrum. With their sufficiently long lifetimes, minimum number of atoms, and simple dissociation paths, DIA MMCs are promising candidates for further experimental and theoretical investigations of multiply charged ion chemistry.

Role of contrast of a relativistic femtosecond laser pulse interacting with solid and structured targets

We consider the effect of a pre-plasma layer inevitably present in experiments on the acceleration of electrons and ions during interaction of a relativistic femtosecond laser pulse with a dense plasma. The interaction regimes are identified in which the presence of such a layer can significantly increase the average and maximum energies of electrons. The regimes are discussed in which an artificial nanosecond prepulse makes it possible to produce a collimated electron beam with a high charge and an average energy of up to 10 ponderomotive energies in the direction of the reflected or incident laser beam. It is shown that the acceleration of ions, as a rule, requires an ultrahigh contrast of the laser pulse, since the parameters of the accelerated ion beams deteriorate significantly in the presence of preplasma or due to the evaporation of a thin-film target. The regimes of interaction of laser pulses with thick targets, in which heavy multiply charged ions can be accelerated by cleaning the surface with a prepulse, are also discussed. An essential part of the review is devoted to the interaction of radiation with micro- and nanostructured targets. Both the methods of their fabrication and the issues related to the interaction of a femtosecond laser pulse and its contrast with such structures are considered.

Engineering spatial correlations of entangled photon pairs by pump beam shaping.

The ability to engineer the properties of quantum optical states is essential for quantum information processing applications. Here, we demonstrate tunable control of spatial correlations between photon pairs produced by spontaneous parametric down-conversion, and measure them using an electron multiplying charge coupled device (EMCCD) camera. By shaping the spatial pump beam profile in a type-I collinear configuration, we tailor the spatial structure of coincidences between photon pairs entangled in high dimensions without effect on intensity. The results highlight fundamental aspects of spatial coherence and hold potential for the development of quantum technologies based on high-dimensional spatial entanglement.

Efficient coupling of picosecond laser pulses with (CCl4)n clusters: Linear vs circular polarization

Ionic outcome and electron energy distribution, upon interaction of carbon tetrachloride clusters ((CCl4)n) with picosecond laser pulses of 1064 nm was investigated, to understand influence of linear and circular polarization on the mechanism of laser-cluster interaction. Contrary to the perception regarding higher proficiency of circular polarized laser pulses in collisional heating of ionized cluster, higher yield of multiply charged atomic ions (up to C5+ (I.E. ~ 392 eV) and Cl10+ (I.E. ~ 456.7 eV)) was obtained for linear polarization. Though marginally higher peak and mean electron energy were recorded for circular polarized laser pulses, with electron energy distribution extending up to ~ 300–350 eV. Present studies provide insight about the crucial steps of complex laser-cluster interaction mechanism, where inverse Bremsstrahlung energization of quasi-free electrons and screening effect within the ionized cluster are found to play a decisive role in determining efficiency of laser-cluster interaction.

Formation and fragmentation of doubly and triply charged ions in the negative ion spectra of neutral N-glycans from viral and other glycoproteins

Structural determination of N-glycans by mass spectrometry is ideally performed by negative ion collision-induced dissociation because the spectra are dominated by cross-ring fragments leading to ions that reveal structural details not available by many other methods. Most glycans form [M – H]- or [M + adduct]- ions but larger ones (above approx. m/z 2000) typically form doubly charged ions. Differences have been reported between the fragmentation of singly and doubly charged ions but a detailed comparison does not appear to have been reported. In addition to [M + adduct]- ions (this paper uses phosphate as the adduct) other doubly, triply, and quadruply charged ions of composition [Mn + (H2PO4)n]n- have been observed in mixtures of N-glycans released from viral and other glycoproteins. This paper explores the formation and fragmentation of these different types of multiply charged ions with particular reference to the presence of diagnostic fragments in the CID spectra and comments on how these ions can be used to characterize these glycans.Graphical abstract

Measuring Electronic Structure of Multiply Charged Anions to Understand Their Chemistry: A Case Study on Gaseous Polyhedral closo-Borate Dianions.

Research on multiply charged anions (MCAs) in the gas phase has been intensively performed during the past decades, mainly to understand fundamental molecular physics phenomena, for example, intramolecular Coulomb repulsion and existence of the repulsive Coulomb barrier. However, the relevance of these investigations with respect to understanding MCAs' chemistry appears often vague. Here, we discuss how insights into the electronic structure obtained from negative ion photoelectron spectroscopy (NIPES) combined with theoretical calculations and collision-induced dissociation can provide a fundamental understanding of the intrinsic chemical reactivity of MCAs and their fragments. This is exemplified in our studies on polyhedral closo-borate dianions [BnXn]2- (n = 6, 10, 11, 12; X = H, F-I, CN) and their fragment ions. For example, the rational design of closo-borate dianions with specific electronic properties is described, which leads to generating highly reactive fragments. Depending on the dianionic precursor, these fragments are tuned to either bind noble gases effectively or activate small molecules like CO and N2. The intrinsic electronic properties of closo-borate dianions are further compared to their electrochemistry in solutions, revealing solvent effects on the redox potentials. Neutral host molecules such as cyclodextrins are found to bind strongly to [BnXn]2-, and gas phase NIPES provides insights into the intrinsic host-guest interactions. Finally, outlooks including the direct NIPES of molecular fragment ions that cannot be generated in the condensed phase and their utilization in preparative mass spectrometry are discussed.

Enhanced ionic conductivity of aluminum tungstate by crystallographic orientation in a strong magnetic field

AbstractThe ionic conduction of multiply charged ions, rather than singly charged ions, is beneficial for energy storage and sensor applications. The low mobility of multiply charged ions is one important obstacle to the implementation of these applications. Chemical methods, such as doping and solid solution formation, have been used to improve ionic conductivity. However, the apparent performance of ceramic electrolytes can be improved by the crystallographic alignment of anisotropic grains. In this study, crystal‐oriented aluminum tungstate ceramics were processed by slip casting in a strong magnetic field. The b‐axis‐ and c‐axis‐oriented aluminum tungstate ceramics can be produced by this technique. The orientation of grains along the b‐axis could enhance ionic conductivity by at least 1.77 times compared to that of a randomly oriented sample and 2.13 times compared to that of the c‐axis‐oriented sample. The results of this study suggest that this method can improve the ionic conductivity of an anisotropic material using polycrystalline processing instead of difficult single‐crystal synthesis techniques.