Charge State Distribution Research Articles

Collisional-radiative modeling for the EUV spectrum of W40+-W42+ions

The wavelengths and transition rates of W40+-W42+ ions within the range of 40–140 Å, have been calculated using the Flexible Atomic Code of the Dirac-Fock-Slater method with a central potential. We investigated the charge state distribution of W38+-W45+ ions at different temperatures by constructing an appropriate rate equation and demonstrate the importance of the dielectronic recombination process. Additionally, we simulated the emission spectra of W40+-W42+ ions in a Tokamak plasma environment using collisional-radiative modeling. Our findings demonstrate strong agreement with experimental results and other related theoretical investigations. Finally, we propose certain pairs of transition lines as diagnostic tools for plasma temperature and density, leveraging the correlation between line intensity ratio and electron temperature and density.

Generation of plasma from multiple targets by laser ion source for TIARA ion implanter

We investigated a laser ion source for use as an ion source for the ion implanter in Takasaki Ion Accelerators for Advanced Radiation Application to increase the number of ion species that can be produced and to enable rapid switching of ion species. Herein, we analyzed the charge state distribution of ions in a laser plasma generated through irradiation of graphite, titanium, copper, and tantalum targets with 30 mJ Nd:YAG laser to determine the particle number of low-charge ions per pulse at 1.1 m from the target. The particle number of singly charged ions could be increased by adjusting the laser power density. For carbon, titanium, and tantalum, the particle numbers were in the order of 1010 ions per pulse, whereas for copper, the particle numbers were in the order of 109, lower than for other target materials.

Nonideal effects on ionization potential depression and ionization balance in dense Al and Au plasmas.

For low-density plasmas, the ionization balance can be properly described by the normal Saha equationin the chemical picture. For dense plasmas, however, nonideal effects due to the interactions between the electrons and ions and among the electrons themselves affect the ionization potential depression and the ionization balance. With the increasing of plasma density, the pressure ionization starts to play a more obvious role and competes with the thermal ionization. Based on a local-density temperature-dependent ion-sphere model, we develop a unified and self-consistent theoretical formalism to simultaneously investigate the ionization potential depression, the ionization balance, and the charge states distributions of the dense plasmas. In this work, we choose Al and Au plasmas as examples as Al is a prototype light element and Au is an important heavy element in many research fields such as in the inertial confinement fusion. The nonideal effect of the free electrons in the plasmas is considered by the single-electron effective potential contributed by both the bound electrons of different charge states and the free electrons in the plasmas. For the Al plasmas, we can reconcile the results of two experiments on measuring the ionization potential depression, in which one experiment can be better explained by the Stewart-Pyatt model while the other fits better with the Ecker-Kröll model. For dense Au plasmas, the results show that the double peak structure of the charge state distribution appears to be a common phenomenon. In particular, the calculated ionization balance shows that the two- and three-peak structures can appear simultaneously for denser Au plasmas above ∼30g/cm^{3}.

Application of a metallic-magnetic calorimeter for high-resolution x-ray spectroscopy of Fe at an EBIT

In this work, we present an experiment conducted at the S-EBIT-I ion trap of GSI. It involved the study of ion-electron collisions of Fe and Ba ions in various charge states with the electron beam. Characteristic x-ray radiation emitted during the continuous interaction was recorded utilizing an energy-dispersive maXs-30 detector based on metallic-magnetic calorimeter (MMC) technology. Optimizations to the applied sensitivity-drift correction and energy calibration procedures significantly improved the achieved energy resolution compared to previous applications of a similar detector. This made it possible to individually resolve and identify overlapping x-ray lines of iron and barium in a wide spectral range. As a demonstration of the outstanding detector performance, we used the recorded spectral data to extract an estimate of the charge state distribution of Fe ions in the trap. This experiment campaign marks an important milestone in the ongoing effort to enable the deployment of MMC detectors for future high-precision measurements in fundamental physics experiments.

X-ray-induced atomic transitions via machine learning: A computational investigation

Intense x-ray free-electron laser pulses can induce multiple sequences of one-photon ionization and accompanying decay processes in atoms, producing highly charged atomic ions. Considering individual quantum states during these processes provides more precise information about the x-ray multiphoton ionization dynamics than the common configuration-based approach. However, in such a state-resolved approach, extremely huge-sized rate-equation calculations are inevitable. Here we present a strategy that embeds machine-learning models into a framework for atomic state-resolved ionization dynamics calculations. Machine learning is employed for the required atomic transition parameters, whose calculations possess the computationally most expensive steps. We find for argon that both feedforward neural networks and random forest regressors can predict these parameters with acceptable, but limited accuracy. State-resolved ionization dynamics of argon, in terms of charge-state distributions and electron and photon spectra, are also presented. Comparing fully calculated and machine-learning-based results, we demonstrate that the proposed machine-learning strategy works in principle and that the performance, in terms of charge-state distributions and electron and photon spectra, is good. Our work establishes a first step toward accelerating the calculation of atomic state-resolved ionization dynamics induced by high-intensity x rays. Published by the American Physical Society 2024

Fullerene C20 carbon nucleation induced by IR ns pulsed laser-generated plasma

Intense laser pulses can be employed to generate plasma, carbon aggregates, and nanoparticles. The plasma produced by ns laser pulses impinging on carbon targets in a vacuum generates carbon vapors, atoms nucleation and growth of nano aggregates. Mass quadrupole spectrometry has permitted to analyze the mass of the carbon atoms and molecules produced in a vacuum by laser-generated plasma, discovering that the fullerene C20 and other small carbon aggregates have a high probability of being produced. In this paper, the conditions of C20 aggregate synthetization are presented, and their yield generation is approximately evaluated. It also calculated the process ablation yield, the maximum carbon energy acquired in the plasma, the plasma temperature and density, the adiabatic plasma expansion velocity, and the carbon ion charge state distributions. To this, measurements of time-of-flight (TOF) of ions have been performed using suitable ion collectors and ion energy analyzers.

Excited states in warm and hot dense matter.

Accurate modeling of warm and hot dense matter is challenging in part due to the multitude of excited states that must be considered. Here, we present a variational framework that models these excited states. In this framework an excited state is defined by a set of effective one-electron occupation factors, and the corresponding energy is defined by the effective one-body energy with an exchange and correlation term. The variational framework is applied to an atom-in-plasma model (a generalization of the so-called average atom model). Comparisons with a density functional theory based average atom model generally reveal good agreement in the calculated pressure, but our model also gives access to the excitation energies and charge state distributions.

Molecular Dynamics Simulations of Native Protein Charging via Proton Transfer during Electrospray Ionization with Grotthuss Diffuse H3O.

Unraveling the mechanism by which native proteins are charged through electrospray ionization (ESI) has been the focus of considerable research because observable charge states can be correlated to biophysical characteristics, such as protein folding and, thus, solution conformation. Difficulties in characterizing electrosprayed droplets have catalyzed the use of molecular dynamics (MD) to provide insights into the mechanisms by which proteins are charged and transferred to the gas phase. However, prior MD studies have utilized metal ions, primarily Na+, as charge carriers, even though proteins are primarily detected as protonated ions in the mass spectra. Here, we propose a modified MD protocol for simulating discrete Grotthuss diffuse H3O+ that is capable of dynamically altering amino-acid protonation states to model electrospray charging and gaseous ion formation of model proteins, ubiquitin, and myoglobin. Application of the protocol to the evaporation of acidic droplets enables a molecular perspective of H3O+ coordination and proton transfer to/from proteins, which is unfeasible with the metal charge carriers used in previous MD studies of ESI. Our protocol recreates experimentally observed charge-state distributions and supports the charge residue model (CRM) as the dominant mechanism of native protein ionization during ESI. Additionally, our results suggest that protonation is highly specific to individual residues and is correlated to the formation of localized hydrated regions on the protein surface as droplets desolvate. Considering the use of discrete H3O+ instead of Na+, the developed protocol is a necessary step toward developing a more comprehensive model of protein ionization during ESI.

Exploiting Charge State Distribution To Probe Intramolecular Interactions in Gas-Phase Phosphopeptides and Enhance Proteomics Analyses.

Charging of analytes is a prerequisite for performing mass spectrometry analysis. In proteomics, electrospray ionization is the dominant technique for this process. Although the observation of differences in the peptide charge state distribution (CSD) is well-known among experimentalists, its analytical value remains underexplored. To investigate the utility of this dimension, we analyzed several public data sets, comprising over 250,000 peptide CSD profiles from the human proteome. We found that the dimensions of the CSD demonstrate high reproducibility across multiple laboratories, mass analyzers, and extensive time intervals. The general observation was that the CSD enabled effective partitioning of the peptide property space, resulting in enhanced discrimination between sequence and constitutional peptide isomers. Next, by evaluating the CSD values of phosphorylated peptides, we were able to differentiate between phosphopeptides that indicate the formation of intramolecular structures in the gas phase and those that do not. The reproducibility of the CSD values (mean cosine similarity above 0.97 for most of the experiments) qualified CSD data suitable to train a deep-learning model capable of accurately predicting CSD values (mean cosine similarity - 0.98). When we applied the CSD dimension to MS1- and MS2-based proteomics experiments, we consistently observed around a 5% increase in protein and peptide identification rate. Even though the CSD dimension is not as effective a discriminator as the widely used retention time dimension, it still holds the potential for application in direct infusion proteomics.

Kinetic energy distributions of atomic ions from disintegration of argon containing nanoclusters in moderately intense nanosecond laser fields: Coulomb explosion or hydrodynamic expansion.

We report kinetic energies (KE) of multiply charged atomic ions (MCAI) from interactions of moderately intense nanosecond lasers at 532 nm with argon containing clusters, including neat and doped clusters with a trace amount of trichlorobenzene. We develop a mathematical method to retrieve speed and thereby kinetic energy information from analyzing the time-of-flight profiles of the MCAI. This method should be generally applicable in detections of energetic charged particles with high velocities, a realm where velocity map imaging is inadequate. From this analysis, we discover that the KE of MCAI from doped clusters demonstrates a quadratic dependence on the charge of the atomic ions, while for neat clusters, the dependence is cubic. This result confirms the nature of the cluster disintegration process to be dominated by Coulomb explosion. This result bears more similarity to reports from extreme vacuum ultraviolet (EUV) fields with similar intensities, than to reports from near infrared (NIR) intense laser fields. However, the charge state distribution from our experiment is the opposite: we observe more higher charge state ions than reported in EUV fields, and our charge state distribution is actually similar to those reported in NIR fields. We also report a significant effect of the external electric field on the charge state distribution of the atomic ions: the presence of an electric field can significantly increase the charge from the atomic ions, as shown by a three-fold reduction in the average kinetic energy per charge. Although molecular dynamics simulations have been implemented for experiments in the EUV and NIR, our results allude to the need of a concerted effort in this regime of moderately intense nanosecond laser fields. The significant decrease in charge state distribution and the significant increase in KE from doped clusters, compared with neat clusters, is a telltale sign that the true interaction time between the laser field and the cluster may be substantially shorter than the duration of the laser, a welcome relief for molecular dynamics simulations.

The role of solvation on the conformational landscape of α-synuclein.

Native ion mobility mass spectrometry has been used extensively to characterize ensembles of intrinsically disordered protein (IDP) conformers, but the extent to which the gaseous measurements provide realistic pictures of the solution conformations for such flexible proteins remains unclear. Therefore, we systematically studied the relationship between the solution and gaseous structural ensembles by measuring electrospray charge state and collision cross section (CCS) distributions for cationic and anionic forms of α-synuclein (αSN), an anionic protein in solution, as well as directly probed gas phase residue to residue distances via ion/ion reactions between gaseous α-synuclein cations and disulfonic acid linkers that form strong electrostatic bonds. We also combined results from in-solution protein crosslinking identified from native tandem mass spectrometry (MS/MS) with an initial αSN ensemble generated computationally by IDPConformerGenerator to generate an experimentally restrained solution ensemble of αSN. CCS distributions were directly calculated for the solution ensembles determined by NMR and compared to predicted gaseous conformers. While charge state and collision cross section distributions are useful for qualitatively describing the relative structural dynamics of proteins and major conformational changes induced by changes to solution states, the predicted and measured gas phase conformers include subpopulations that are significantly different than those expected from completely "freezing" solution conformations and preserving them in the gas phase. However, insights were gained on the various roles of solvent in stabilizing various conformers for extremely dynamic proteins like α-synuclein.

Solar wind ion charge state distributions and compound cross sections for solar wind charge exchange X-ray emission

Solar wind ion charge state distributions and compound cross sections for solar wind charge exchange X-ray emission

Uncovering Distinct Peptide Charging Behaviors in Electrospray Ionization Mass Spectrometry Using a Large-Scale Dataset.

Electrospray ionization is a powerful and prevalent technique used to ionize analytes in mass spectrometry. The distribution of charges that an analyte receives (charge state distribution, CSD) is an important consideration for interpreting mass spectra. However, due to an incomplete understanding of the ionization mechanism, the analyte properties that influence CSDs are not fully understood. Here, we employ a machine learning-based approach and analyze CSDs of hundreds of thousands of peptides. Interestingly, half of the peptides exhibit charges that differ from what one would naively expect (the number of basic sites). We find that these peptides can be classified into two regimes (undercharging and overcharging) and that these two regimes display markedly different charging characteristics. Notably, peptides in the overcharging regime show minimal dependence on basic site count, and more generally, the two regimes exhibit distinct sequence determinants. These findings highlight the rich ionization behavior of peptides and the potential of CSDs for enhancing peptide identification.

Effects of Amino Acid Additives on Protein Stability during Electrothermal Supercharging in ESI-MS.

The surprising formation of highly charged protein ions from aqueous ammonium bicarbonate solution is a fascinating phenomenon referred to as electrothermal supercharging (ETS). Although the precise mechanism involved is not clearly understood, previous studies predominantly suggest that ETS is due to native protein destabilization in the presence of bicarbonate anion inside the electrospray ionization droplets under high temperatures and spray voltages. To evaluate existing hypotheses surrounding the underlying mechanism of ETS, the effects of several additives on protein charging under ETS conditions were investigated. The changes in the protein charge state distributions were compared by measuring the ratios between the intensities of highest intensity charge states of native and unfolded protein envelopes and shifts in the lowest and highest observed charge states. This study demonstrated that source temperature plays a more important role in ETS compared to spray voltage, especially when using a nebulized microelectrospray ionization source. Moreover, the effect of amino acids on ETS were generally in good agreement with the extensive literature available on the stabilization or destabilization of proteins by these additives in bulk solution. Among the natural amino acids, protein supercharging was significantly reduced by proline and glycine; however, imidazole provided the highest degree of noncovalent complex stabilization against ETS, outperforming the amino acids. Overall, our study shows that the simple addition of stabilizing reagents such as proline and imidazole can reduce the extent of apparent protein unfolding and supercharging in ammonium bicarbonate solution and provide evidence against the roles of charge depletion and thermal unfolding during ETS.

Top/Middle-Down Characterization of α-Synuclein Glycoforms.

α-Synuclein is an intrinsically disordered protein that plays a critical role in the pathogenesis of neurodegenerative disorders, such as Parkinson's disease. Proteomics studies of human brain samples have associated the modification of the O-linked N-acetyl-glucosamine (O-GlcNAc) to several synucleinopathies; in particular, the position of the O-GlcNAc can regulate protein aggregation and subsequent cell toxicity. There is a need for site specific O-GlcNAc α-synuclein screening tools to direct better therapeutic strategies. In the present work, for the first time, the potential of fast, high-resolution trapped ion mobility spectrometry (TIMS) preseparation in tandem with mass spectrometry assisted by an electromagnetostatic (EMS) cell, capable of electron capture dissociation (ECD), and ultraviolet photodissociation (213 nm UVPD) is illustrated for the characterization of α-synuclein positional glycoforms: T72, T75, T81, and S87 modified with a single O-GlcNAc. Top-down 213 nm UVPD and ECD MS/MS experiments of the intact proteoforms showed specific product ions for each α-synuclein glycoforms associated with the O-GlcNAc position with a sequence coverage of ∼68 and ∼82%, respectively. TIMS-MS profiles of α-synuclein and the four glycoforms exhibited large structural heterogeneity and signature patterns across the 8+-15+ charge state distribution; however, while the α-synuclein positional glycoforms showed signature mobility profiles, they were only partially separated in the mobility domain. Moreover, a middle-down approach based on the Val40-Phe94 (55 residues) chymotrypsin proteolytic product using tandem TIMS-q-ECD-TOF MS/MS permitted the separation of the parent positional isomeric glycoforms. The ECD fragmentation of the ion mobility and m/z separated isomeric Val40-Phe94 proteolytic peptides with single O-GlcNAc in the T72, T75, T81, and S87 positions provided the O-GlcNAc confirmation and positional assignment with a sequence coverage of ∼80%. This method enables the high-throughput screening of positional glycoforms and further enhances the structural mass spectrometry toolbox with fast, high-resolution mobility separations and 213 nm UVPD and ECD fragmentation capabilities.

Online Bipolar Dual Spray for the Charge State Reduction and Characterization of Complex Synthetic Polymers.

Charge reduction mass spectrometry (CR/MS) hyphenated to liquid chromatography (LC) couples liquid-phase compound separation and mass spectral decompression to resolve and characterize multicomponent systems. LC/CR/MS has proven to be effective for complex mixture analysis, particularly synthetic polymers. A newer charge manipulation approach called bipolar dual spray has previously been demonstrated to reduce the observed charge state distribution of ammoniated polyethene glycol. In this approach, two electrospray emitters, in close proximity and of opposite polarity, fuse droplets from their electrospray plumes, which allows the subsequent chemistry. In this work, we investigate the ability of bipolar dual spray to reduce the charge of synthetic polyols, thereby simplifying complex mixture analysis and generating new compositional information only available through the coupling of charge reduction with LC/MS analysis. This work also represents the first demonstration of online charge reduction via dual spray. Polyethylene glycol (PEG) 7.2K subjected to LC/MS with dual spray reduced the average charge state from 8.2+ to 4.4+. LC/MS with dual spray was also applied to the characterization of an end-group-modified PEG 10K (i.e., aminated) containing several reaction impurities. This approach allowed for the identification of low-level starting material, tosylated PEG, and PEG mono(amine), where both LC/MS and direct infusion dual spray did not detect the impurities. Overall, the results demonstrated that bipolar dual spray can be incorporated into an LC/MS analysis and affords the ability to reduce the charge state distribution of PEG cations, decompress the m/z axis, lower spectra complexity, and enable/simplify data interpretation.

Time-dependent photoionization spectroscopy of the Seyfert galaxy NGC 3783

We present an investigation into the spectroscopic properties of non-equilibrium photoionization processes operating in a time-evolving mode. Through a quantitative comparison between equilibrium and time-evolving models, we find that the time-evolving model exhibits a broader distribution of charge states, accompanied by a slight shift in the peak ionization state depending on the source variability and gas density. The time-evolving code tpho in SPEX was successfully employed to analyze the spectral properties of warm absorbers in the Seyfert galaxy NGC 3783. The incorporation of variability in the tpho model improves the fits of the time-integrated spectra, providing more accurate descriptions of the average charge states of several elements, in particular Fe, which is peaked around Fe XIX. The inferred densities and distances of the relevant X-ray absorber components are estimated to be approximately a few times 1011 m−3 and ≤1 pc, respectively. Furthermore, the updated fit suggests a potential scenario in which the observed absorbers are being expelled from the central active galactic nucleus at the escape velocities. This implies that these absorbers might not play a significant role in the active galactic nucleus feedback mechanism.

A method for calculating the radiation characteristics of nonequilibrium laboratory plasmas

One of the fundamentally important issues in the characterization of a dense high-temperature plasma is the description of its self-radiation aimed at determining the radiation losses and their spectral composition. In this paper, a new method is proposed for calculating the radiation characteristics of a high-temperature nonequilibrium plasma. The method is based on a collisional radiative model, which makes it possible to calculate the charge-state distribution in the plasma and the excited-state distribution of the plasma ions. The transfer equations are solved separately for the radiation with a continuous spectrum, combining the bremsstrahlung and recombination radiation spectra, and for the spectral line radiation. A feature of the method is that, when calculating the mean line absorption coefficients, dimensionless weighting coefficients are used, which make it possible to take into account the contribution of the strongest lines. The use of weighting coefficients has the result that even a one-group approximation yields good agreement with the numerical solution of the complete spectral problem.

2D X-ray Fluorescence Imaging as a Probe for Charge State Distribution of Manganese in Aged MnHCF-Based Electrodes

2D X-ray Fluorescence Imaging as a Probe for Charge State Distribution of Manganese in Aged MnHCF-Based Electrodes

Accurate simultaneous lead stopping power and charge-state measurements in gases and solids: Benchmark data for basic atomic theory and nuclear applications

We have measured for the first time simultaneously both the mean charge states and stopping powers of (35–280) MeV/u 208Pb ions in gases and solids with an accuracy of 1%. The existence at lower energies and disappearance at higher of density effects in the charge-state distribution and the corresponding stopping power are directly confirmed and comparisons with widely used theories and simulations for heavy ions demonstrate strong deviations of up to 27%. However, an unprecedented prediction power of better than 3% has been achieved for the energy loss when the measured mean charge-states are implemented in the Lindhard-Sørensen theory. Our present benchmark data contribute to an improved understanding of the basic atomic collision processes and to numerous applications in nuclear physics. Extending the GANIL data [1] to higher accuracy and energies, we can now answer at which velocities the Bohr-Lindhard density effect in stopping will vanish.