Two-step Ionization Research Articles

Resonance ionization spectroscopy of neodymium for determining a highly efficient two-step ionization scheme

Two-color two-step resonance ionization spectroscopy of neodymium (Nd) was performed to identify more than 120 even-parity autoionizing levels and their candidate J-values. The analysis of the observed autoionizing Rydberg series yielded a value of 44,560.11 (43)stat (2)sys cm−1 as a more accurate ionization potential of Nd. The saturation method was used to measure the transition cross-sections for some intense ionization transitions. From the measured cross-sections, the ionization efficiencies of some two-step ionization schemes were evaluated using the scheme cross-section formula to obtain several promising schemes.

Resonant laser ionization of neptunium: investigation on excitation schemes and the first ionization potential

The atomic structure of neptunium (Np) was investigated by two-step resonance ionization spectroscopy. The study involved exploring ground-state transitions as well as following transitions to high-lying states just below the ionization potential (IP) or auto-ionizing states above the IP. That resulted in the identification of two-step ionization schemes, suitable for trace analysis and nuclear structure investigations. The lifetimes of two excited states located at 25,342.48 cm-1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\, \ ext {cm}^{-1} $$\\end{document} and 25,277.64 cm-1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\, \ ext {cm}^{-1} $$\\end{document} were determined as 230(12) ns and 173(9) ns, respectively. Because of the absence of Rydberg series in wide-ranging spectra recorded, the first IP was determined through the field ionization of high-lying, weakly-bound states using a well-controlled static electric field. By applying the saddle-point model, an IP value of 50,535.54(15) cm-1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{-1}$$\\end{document} [6.265608(19) eV] was derived. This value agrees with the current literature value of 50,535(2) cm-1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{-1}$$\\end{document}, while providing a more than ten times higher precision.Graphic abstract

Target Development towards First Production of High-Molar- Activity 44gSc and 47Sc by Mass Separation at CERN-MEDICIS.

The radionuclides 43Sc, 44g/mSc, and 47Sc can be produced cost-effectively in sufficient yield for medical research and applications by irradiating natTi and natV target materials with protons. Maximizing the production yield of the therapeutic 47Sc in the highest cross section energy range of 24-70 MeV results in the co-production of long-lived, high-γ-ray-energy 46Sc and 48Sc contaminants if one does not use enriched target materials. Mass separation can be used to obtain high molar activity and isotopically pure Sc radionuclides from natural target materials; however, suitable operational conditions to obtain relevant activity released from irradiated natTi and natV have not yet been established at CERN-MEDICIS and ISOLDE. The objective of this work was to develop target units for the production, release, and purification of Sc radionuclides by mass separation as well as to investigate target materials for the mass separation that are compatible with high-yield Sc radionuclide production in the 9-70 MeV proton energy range. In this study, the in-target production yield obtained at MEDICIS with 1.4 GeV protons is compared with the production yield that can be reached with commercially available cyclotrons. The thick-target materials were irradiated at MEDICIS and comprised of metallic natTi, natV metallic foils, and natTiC pellets. The produced radionuclides were subsequently released, ionized, and extracted from various target and ion source units and mass separated. Mono-atomic Sc laser and molecule ionization with forced-electron-beam-induced arc-discharge ion sources were investigated. Sc radionuclide production in thick natTi and natV targets at MEDICIS is equivalent to low- to medium-energy cyclotron-irradiated targets at medically relevant yields, furthermore benefiting from the mass separation possibility. A two-step laser resonance ionization scheme was used to obtain mono-atomic Sc ion beams. Sc radionuclide release from irradiated target units most effectively could be promoted by volatile scandium fluoride formation. Thus, isotopically pure 44g/mSc, 46Sc, and 47Sc were obtained as mono-atomic and molecular ScF 2+ ion beams and collected for the first time at CERN-MEDICIS. Among all the investigated target materials, natTiC is the most suitable target material for Sc mass separation as molecular halide beams, due to high possible operating temperatures and sustained release.

Investigation of the significance of excited species in wave-heated dense non-ideal microplasmas using particle-in-cell Monte Carlo-collision modeling

A computational model for the interaction of a high-pressure microplasma with an electromagnetic wave is presented. A one-dimensional particle-in-cell Monte Carlo collision model is used to investigate the plasma non-ideality effects in a second-stage laser-heated xenon plasma with a comprehensive chemistry mechanism, including excited species. A xenon microplasma at a temperature of 300 K and pressure of 10 bar becomes non-ideal after the laser heating stage with lower ionization and electronic excitation barriers, which makes the presence of excited species important to the plasma generation process. For these conditions, two-step ionization via excited species becomes a major contributor to plasma ionization. We find that full ionization of the plasma is obtained in ∼2 ps when excited species are included in the chemistry model, as opposed to ∼2.5 ps for a chemistry mechanism that does not consider their effect. With excited species, the ionization mode transitions from direct ionization via electron-neutral collisions to direct and stepwise ionization as the plasma generation progresses.

Offline commissioning of a new gas cell for the MARA Low-Energy Branch

Results of offline commissioning tests for a new dedicated gas cell for the Mass Analysing Recoil Apparatus (MARA) Low-Energy Branch are reported. Evacuation time, ion survival and transport efficiency in helium buffer gas were characterized with a radioactive 223Raα-recoil source. Suppression of the ion signal, originating from non-neutralized species in the gas cell, was explored with 219Rn ions, the daughter recoil of 223Ra, as a function of voltage applied to one of the ion-collector electrodes. Two-step laser resonance ionization of stable tin isotopes produced inside the gas cell from a heated bronze filament was demonstrated, and broadening of the atomic resonances in argon buffer gas was studied. These tests indicate the suitability of the new gas cell for future in-gas laser spectroscopy studies of exotic nuclei at the Accelerator Laboratory of the University of Jyväskylä.

Probing the Atomic Structure of Californium by Resonance Ionization Spectroscopy

The atomic structure of californium is probed by two-step resonance ionization spectroscopy. Using samples with a total amount of about 2×1010 Cf atoms (ca. 8.3 pg), ground-state transitions as well as transitions to high-lying Rydberg states and auto-ionizing states above the ionization potential are investigated and the lifetimes of various atomic levels are measured. These investigations lead to the identification of efficient ionization schemes, important for trace analysis and nuclear structure investigations. Most of the measurements are conducted on 250Cf. In addition, the isotope shift of the isotopic chain 249−252Cf is measured for one transition. The identification and analysis of Rydberg series enables the determination of the first ionization potential of californium to EIP=50,666.76(5)cm−1. This is about a factor of 20 more precise than the current literature value.

Analytical Solving a Nonlinear Model of the Glow Discharge

A nonlinear model has been introduced for the positive column of DC glow discharge in apure sealed, or low flow, gas media by including the diffusion, recombination, attachment, detachment,process and having the two-step ionization process of the metastable excited states, too. By thecombination of the system of the nonlinear continuity equations of the system, using some physicalestimations, and degrading the resulted nonlinear PDE in polar and rectangular systems of coordinatethe steady-state nonlinear ODE have been derived. Using a series-based solution, an innovativenonlinear recursion relation has been proposed for calculating the sentence of series. Using the stateof elimination of free charge on the outer boundary of the discharge vessel, the universal equation ofthe characteristic energy of the electrons versus the similarity variable, using the maximum degree ofionization as the parameter, has been derived.

Up-conversion charging dynamics exampled by Mn<sup>2+</sup>-activated persistent phosphor

Persistent phosphor as a kind of light-emitting material can store excitation energy in the so-called traps, and then persistently release the energy in the form of light emission after the end of excitation. This emission is called persistent luminescence. Much attention has been paid to optimizing the emission performance of persistent phosphors, including emission wavelength and persistent time. However, research on the excitation for charging persistent phosphors is relatively lacking. To acquire the persistent luminescence effectively, the traps need to be filled typically by ionizing irradiation. That is, high-energy light (such as ultraviolet light) is a general requirement for charging the persistent phosphors. Taking into account the fact that low-energy illumination (e.g. visible or infrared light) is much more suitable and less harmful than ultraviolet light for some practical applications, taking advantage of the low-energy light excitation is therefore an urgent issue to be solved in the persistent luminescence area. Several low-energy excitation approaches have been reported, in which up-conversion charging (UCC) is a promising candidate for charging phosphors using low-energy excitation light sources. The definition of UCC is as follows: UCC is a non-linear excitation for storage phosphors, in which the traps are typically filled via a two-step ionization mechanism. Prior research on the UCC has focused primarily on the demonstration of two-step ionization and the associated trapping properties. Recently, researchers have realized that the excitation light may release some trapped electrons while filling the traps (i.e. excitation-light stimulated detrapping). Competition between the trapping and detrapping during the UCC has been roughly described on the assumption that the illumination dose is in a certain range and the effect of ambient-temperature stimulated detrapping is negligible. Despite the initial progress, the exact effect of detrapping on the UCC process needs to be further explored. Here we demonstrate the effect of detrapping on UCC dynamics by a rate equation approach. Accordingly, taking LaMgGa<sub>11</sub>O<sub>19</sub>:Mn<sup>2+</sup> phosphor illuminated by a 450 nm laser for example, we measure its thermoluminescence. Our measurements reveal that the competition between the trapping and detrapping depends both on illumination power and on illumination duration. The experimental results are consistent well with the theoretical predictions, thereby offering a new insight into the understanding of UCC. In addition, the experimental demonstration on the LaMgGa<sub>11</sub>O<sub>19</sub>:Mn<sup>2+</sup> phosphor allows us to explore the generality of the present UCC model. Accordingly, we expect some existing phosphors can now be revisited.

Recent Advances of Ambient Mass Spectrometry Imaging and Its Applications in Lipid and Metabolite Analysis.

Ambient mass spectrometry imaging (AMSI) has attracted much attention in recent years. As a kind of unlabeled molecular imaging technique, AMSI can enable in situ visualization of a large number of compounds in biological tissue sections in ambient conditions. In this review, the developments of various AMSI techniques are discussed according to one-step and two-step ionization strategies. In addition, recent applications of AMSI for lipid and metabolite analysis (from 2016 to 2021) in disease diagnosis, animal model research, plant science, drug metabolism and toxicology research, etc., are summarized. Finally, further perspectives of AMSI in spatial resolution, sensitivity, quantitative ability, convenience and software development are proposed.

Terbium Medical Radioisotope Production: Laser Resonance Ionization Scheme Development.

Terbium (Tb) is a promising element for the theranostic approach in nuclear medicine. The new CERN-MEDICIS facility aims for production of its medical radioisotopes to support related R&D projects in biomedicine. The use of laser resonance ionization is essential to provide radioisotopic yields of highest quantity and quality, specifically regarding purity. This paper presents the results of preparation and characterization of a suitable two-step laser resonance ionization process for Tb. By resonance excitation via an auto-ionizing level, the high ionization efficiency of 53% was achieved. To simulate realistic production conditions for Tb radioisotopes, the influence of a surplus of Gd atoms, which is a typical target material for Tb generation, was considered, showing the necessity of radiochemical purification procedures before mass separation. Nevertheless, a 10-fold enhancement of the Tb ion beam using laser resonance ionization was observed even with Gd:Tb atomic ratio of 100:1.

Odd-parity autoionizing levels of uranium observed by two-color two-step photoionization optogalvanic spectroscopy

Two-color two-step photoionization optogalvanic spectroscopy was performed using high-repetition-rate titanium sapphire lasers and a uranium hollow cathode lamp to find the two-step resonance ionization schemes of uranium. Many ionization transitions were observed by exciting uranium atoms in a ground state into five, even parity, excited levels with the first-step laser and by scanning the second-step laser wavelengths. By blocking the first-step laser, single-color, two-photon ionization transitions were also identified. From these results, we have found more than 50 odd-parity autoionizing levels of uranium in the energy, ranging from the ionization potential (49958.4 cm−1) to 51 150 cm−1. The determined energy levels are within ∼±1 cm−1 of previously reported values.

Multiple fragmentation mechanisms in ammonia: Collisions with protons in the intermediate velocity regime

The ionization and dissociation of ammonia by impact of protons is investigated experimentally in a wide range of energies from 125 to 2700 keV. Coincidence measurements are used to separate single from multiple ionization. The role of the charge sign of the projectile was analyzed for the ionization by comparing the proton with previous electron data. The energy dependence of the single and multiple-ionization cross sections allowed us to evaluate the role of second-order mechanisms. For single ionization, the role of a two-step mechanism was inferred. The double-ionization cross section showed that postcollisional deexcitation takes over the two-step sequential ionization above 800 keV. Triple ionization is prompted mostly by postcollisional Auger decay.

Molecular content of nascent soot: Family characterization using two-step laser desorption laser ionization mass spectrometry

Molecules constituting nascent soot particles have been analyzed by two-step laser desorption laser ionization mass spectrometry. Three samples have been collected from a slightly sooting ethylene/air premixed flame with the aim to investigate soot composition in the transition from nucleated to just-grown soot particles. Sampling locations have been selected based on the evolution of the particle size distribution along the flame axis. The mass spectrometric results point to a strong evolution of the molecular composition. Just-nucleated soot is rich in polycyclic aromatic hydrocarbons (PAHs) dominated by medium sizes from 18 to 40 carbon atoms but containing sizes as large as 90 carbon atoms. Most abundant PAHs are in the form of peri-condensed structures. The presence of a large fraction of odd numbered carbon species shows that pentagonal cycles are a common feature of the detected population. Increasing the distance from the burner outlet, i.e., the particle residence time in flame, leads to an evolution of the chemical composition of this population with a major contribution of carbon clusters including also fullerenes up to about 160 carbon atoms. Our data support a scenario in which large PAHs containing pentagonal rings evolve very efficiently upon thermal processing by a series of dehydrogenation and isomerization processes to form fullerenes. This chemistry happens in the early steps of soot growth showing that carbonization is already active at this stage.

Highly selective two-step laser ionization schemes for the analysis of actinide mixtures

Resonance ionization mass spectroscopy has proven to be a very efficient and selective method for the spatially resolved ultratrace determination of actinide contaminations, and the analysis of specific element and isotopic distributions on surfaces and environment particles. We report on the identification of highly element-selective optical excitation schemes identified for this purpose, with a particular focus on the precise determination of the isobaric ratios of 235U to 239Pu as well as 243Am to 241Pu. The chosen two-step ionization schemes were characterized with respect to their element selectivity on synthetic multi-element actinide mixtures, with an element ratio Pu : Am : U of 1 : 10 : 104, a composition which is typical, e.g., for spent nuclear reactor fuels.

Excitation energies expressed as orbital energies of Kohn-Sham density functional theory with long-range corrected functionals.

A new simple and conceptual theoretical scheme is proposed for estimating one-electron excitation energies using Kohn-Sham (KS) solutions. One-electron transitions that are dominated by the promotion from one initially occupied orbital to one unoccupied orbital of a molecular system can be expressed in a two-step process, ionization, and electron attachment. KS with long-range corrected (LC) functionals satisfies Janak's theorem and LC total energy varies almost linearly as a function of its fractional occupation number between the integer electron points. Thus, LC reproduces ionization energies (IPs) and electron affinities (EAs) with high accuracy and one-electron excitation energies are expressed as the difference between the occupied orbital energy of a neutral molecule and the corresponding unoccupied orbital energy of its cation. Two such expressions can be used, with one employing the orbital energies for the neutral and cationic systems, while the other utilizes orbital energies of just the cation. Because the EA of a molecule is the IP of its anion, if we utilize this identity, the two expressions coincide and give the same excitation energies. Reasonable results are obtained for valence and core excitations using only orbital energies.

Efficient two-color two-step laser ionization schemes of λ1∼ 250 nm and λ2 = 307.9 nm for heavy refractory elements-Measurements of ionization cross-sections and hyperfine spectra of tantalum and tungsten.

We demonstrated efficient two-color two-step laser ionization schemes in the combined use of λ1 ∼ 250 nm and λ2 = 307.9 nm, which are applicable to heavy refractory elements with an atomic number in the wide range of Z = 69-78. We investigated newly observed ionization schemes of tantalum and tungsten atoms in an argon-gas-cell-based laser ion source for the efficient ionization of atoms of unstable nuclei through the two-color two-step laser resonance ionization technique. We experimentally determined the ionization cross sections from the measured saturation curves by solving the rate equations for the ground, intermediate, and ionization continuum populations. Hyperfine structures of these elements were also studied to deduce the isotope-shift, pressure-shift, and pressure-broadening in the resonance spectra of the excitation transitions in the argon gas cell. The electronic factor F255 of the excitation transition λ1 = 255.2115 nm between the ground and intermediate states was deduced from the measured isotope shifts of stable 182,183,184,186W isotopes. The ionization schemes investigated here are applicable to extract any isotopes of these elements by considering the measured pressure shift and nuclear isotope shift in optimizing the wavelength λ1.

Highly efficient isotope separation and ion implantation of 163Ho for the ECHo project

The effective electron neutrino mass measurement at the ECHo experiment requires high purity $^{163}$Ho, which is ion implanted into detector absorbers. To meet the project specifications in efficiency and purity, the entire process chain of ionization, isotope separation, and implantation of $^{163}$Ho was optimized. A new two-step resonant laser ionization scheme was established at the $30\, kV$ magnetic mass separator RISIKO. This achieved ionization and separation efficiencies with an average of $69(5)_\textrm{stat}(4)_\textrm{sys}\,\%$ using intra-cavity frequency doubled Ti:sapphire lasers. The implantation of a $^{166\textrm{m}}$Ho impurity is suppressed about five orders of magnitude by the mass separation. A dedicated implantation stage with focusing and scanning capability enhances the geometric implantation efficiency into the ECHo detectors to $20(2)\,\%$.

Spatially Shaped Laser Pulses for the Simultaneous Detection of Polycyclic Aromatic Hydrocarbons as well as Positive and Negative Inorganic Ions in Single Particle Mass Spectrometry.

Polycyclic aromatic hydrocarbons (PAHs) are toxic organic trace components in atmospheric aerosols that have impacts on climate and human health. They are bound to airborne particles and transported over long distances. Observations of their distribution, transport pathways, and degradation are crucial for risk assessment and mitigation. Such estimates would benefit from online detection of PAHs along with analysis of the carrying particles to identify the source. Typically, laser desorption/ionization (LDI) in a bipolar mass spectrometer reveals the inorganic constituents and provides limited molecular information. In contrast, two-step ionization approaches produce detailed PAH mass spectra from individual particles but without the source-specific inorganic composition. Here we report a new technique that yields the single-particle PAH composition along with both positive and negative inorganic ions via LDI. Thus, the complete particle characterization and source apportionment from conventional bipolar LDI-analysis becomes possible, combined with a detailed PAH spectrum for the same particle. The key idea of the method is spatiotemporal matching of the ionization laser pulse to the transient component distribution in the particle plume after laser desorption. The technique is robust and field-deployable with only slightly higher costs and complexity compared to two-step approaches. We demonstrate its capability to reveal the PAH-distribution on different particle types in combustion aerosols and ambient air.

A mitochondrial-targeted fluorescent probe to sense pH and HOCl in living cells

A series of rosamine dyes were designed and synthesized through one-step reaction. Among them, bifunctional fluorescent probe RosPO(OH)2 showed excellent water solubility and large molar extinction coefficient. RosPO(OH)2 underwent a two-step ionization process as the pH value of the HEPES buffer increased, accompanied a blue shift of UV absorption and an enhancement of fluorescence intensity. This means it can be used as a pH sensor. After the addition of HOCl, the fluorescence of RosPO(OH)2 was quenched and the color of the solution changed from pink to colorless which permitted "naked eye" detection. RosPO(OH)2 could be used as a sensor for detecting HOCl with high selectivity, rapid response, low detection limit (52 nM) and a wide range of pH application (pH 1–10). Colocalization results showed that RosPO(OH)2 could specifically stain in mitochondria. Due to the low toxicity and the excellent water solubility of RosPO(OH)2, it had been successfully applied to image pH and HOCl in living cells.

Experimental investigation of plasma parameters in 13.56 MHz/2 MHz cylindrical inductively coupled plasma

Inductively coupled plasmais widely used in semiconductor and display process because of its desirable characteristics such as high plasma density, simple structure and independently controllable ion energy. The driving frequency is a significant parameter that generates and maintains the plasma. However, the effects of different driving frequencies on the radial distribution of the plasma parameters are hardly investigated. So a large area cylindrical inductively coupled plasma source driven separately by 2 MHz and 13.56 MHz is investigated. In order to perform a comprehensive investigation about the effect of driving frequency, the radially resolved measurements of electron density, electron temperature and density of metastable state atoms for the argon discharge are systematically analyzed by Langmuir double probe and optical emission spectroscopy at various power values and gas pressures. It is found that input power values at high frequency (13.56 MHz) and low frequency (2 MHz) have different effects on plasma parameters. When discharge is driven at high frequency, the electron density increases obviously with the increase of power. However, when discharge is driven at low frequency, the electron temperature increases evidently with the increase of power. This can be explained by calculating the skin depths in high and low frequency discharge. When the discharge is driven at high frequency, the induced electromagnetic field is higher than that at low frequency, and the single electron obtains more energy. It is easier to ionize, so the energy is mainly used to increase the electron density. When the discharge is driven at low frequency, the skin layer is thicker, the number of heated electrons is larger, and the average energy of electrons is increased, so the energy is mainly used to raise the electron temperature. At a gas pressure of 10 Pa, the electron density shows a ‘convex’ distribution and increases with the increase of input power for both the high-frequency and low-frequency discharge. While the distributions of electron temperature are obviously different. When the discharge is driven at high frequency, the electron temperature is relatively flat in the center of the chamber and slightly increases on the edge. When the discharge is driven at low frequency, the electron temperature gradually decreases along the radial position. This is due to the one-step ionization in the high-frequency discharge and the two-step ionization in the low-frequency discharge. In order to prove that the low-frequency discharge is dominated by two-step ionization, the spectral intensities of the argon plasma under the same discharge conditions are diagnosed by optical emission spectroscopy. The number density of metastable states is calculated by the branch ratio method. The results are consistent with the analyses. At a gas pressure of 100 Pa, the electron density increases and then decreases with the increase of radial distance, and the overall distribution shows a " saddle shape” for high frequency and also for low frequency discharge. Although the uniformity of electron density improves with the gas pressure, the uniformity at low frequency is better than that at high frequency. The reason can be attributed to the fact that the skin layer of low frequency is thicker and the heating area is wider.