Stable Negative Ions Research Articles

Rigorous Negative Ion Binding Energies in Low-Energy Electron Elastic Collisions with Heavy Multi-Electron Atoms and Fullerene Molecules: Validation of Electron Affinities

Dramatically sharp resonances manifesting stable negative ion formation characterize Regge pole-calculated low-energy electron elastic total cross sections (TCSs) of heavy multi-electron systems. The novelty of the Regge pole analysis is in the extraction of rigorous and unambiguous negative ion binding energies (BEs), corresponding to the measured electron affinities (EAs) of the investigated multi-electron systems. The measured EAs have engendered the crucial question: is the EA of multi-electron atoms and fullerene molecules identified with the BE of the attached electron in the ground, metastable or excited state of the formed negative ion during a collision? Inconsistencies in the meaning of the measured EAs are elucidated and new EA values for Bk, Cf, Fm, and Lr are presented.

Scavenger hunt: Searching for the optimal target material for low-level 210Pb accelerator mass spectrometry

The Centre of Excellence for Dark Matter Particle Physics aims to measure 210Pb (half-life of 22.2 years) in 1 kg of NaI via accelerator mass spectrometry (AMS) for the SABRE (Sodium iodide with Active Background REjection) South dark matter experiment. The first step is to find the optimal target material (chemical compound and binder) to produce the highest and most stable negative ion output. We initially studied the outputs from Pb3O4, PbO and PbF2 mixed 1:2 with Ag. The 208PbO2− and 208PbF3− currents were 0.5–1.2 μA with the procedural PbF2 compound performing slightly better. Based on these results, we explored the performance of PbF2 mixed with fluorinating agents such as AgF, AgF2 and SbF3 at different ratios. The 1:1 mixture was the best for all additives. The possibility of using either Fe (oxide/fluoride) or NaF as bulk material for the AMS target was also studied, however, none proved suitable.

100 s negative ion accelerations for the JT-60SA negative-ion-based neutral beam injector

In the negative-ion-based neutral beam injector (N-NBI) of JT-60SA, a hydrogen negative ion beam with energy of 500 keV and a current density of 154 A m−2 for 118 s has been successfully demonstrated. This achievement exceeds the requirements (500 keV, 130 A m−2, 100 s) for the first time. To maintain stable negative ion production for a long pulse, the optimal temperatures of the chamber wall and plasma grid were analytically examined and were experimentally demonstrated. It was confirmed that the temperature during the beam pulse should be <50 °C for the chamber wall and >200 °C for the plasma grid. Damage to the filament cathode due to an abnormal discharge, so-called arcing, has been mitigated by developing a fast cut-off system of the arc current for around 100 μs after the arcing. To maintain sufficient voltage holding capability and to reduce the grid heat load due to the beam in the accelerator, techniques developed for the beam acceleration have been applied to this test. As a result of the integration of these techniques, a stable beam over 100 s has been demonstrated successfully. This is the first achievement over a 100 s stable beam with intensity of >75 MW m−2, which is the required practical level in the N-NBI. These results contribute to the coming NBI system for ITER and DEMO.

NNBI for ITER: status of long pulses in deuterium at the test facilities BATMAN Upgrade and ELISE

For the D-T operational phase of the international fusion experiment ITER, starting in 2035, pulses are planned with Q > 10 and a duration of 400 s and pulses with Q = 5 for up to 3600 s. The two neutral beam injection (NBI) systems will deliver 33.3 MW of heating power to the plasma and will also be an important source for non-inductive current drive. An essential part of the NBI systems is a large RF driven source for negative hydrogen or deuterium ions. In order to fulfil the requirements imposed to the NBI system, the ion source has to deliver an intense, stable and homogeneous large negative ion beam over pulse lengths of 400 s or 3600 s. Till now, long pulses in deuterium at the extracted negative ion current density required for ITER could not be demonstrated. The achievable performance is limited by a high current and a pronounced vertical asymmetry of the co-extracted electrons, both strongly increasing with time, whereas the stability of the negative deuterium ions is not an issue. For reduced performance, i.e. reduced negative ion current, lower and more stable co-extracted electron currents are observed, making possible pulses up to 3600 s (using pulsed extraction). One main aim of ongoing investigations at the two test facilities BATMAN Upgrade (Bavarian test machine for negative ions) and ELISE (extraction from a large ion source experiment) is the development of scenarios stabilizing and symmetrizing the co-extracted electron current in deuterium. These investigations are discussed and the current status of hardware upgrades ongoing at BATMAN Upgrade and ELISE towards the ITER scenario of one-hour steady state extraction is presented.

Analysis of the cesium distribution in the JT-60SA negative ion sources for steady long-pulse operation.

To realize stable negative ion beams for 100 s required in the neutral beam injector of JT-60SA, a physical model to control cesium (Cs) distribution inside the negative ion source has been developed in order to maintain the stable negative ion production at the plasma grid (PG) surface with Cs. In this work, to quantitatively evaluate Cs coverage on the PG, a three-dimensional Cs transportation code was introduced to consider the spatial Cs distribution in the source. The spatial temperature distribution of the chamber wall was also introduced in this model. As a result, the reasonable variation of the Cs coverage for 100 s was obtained, compared to that in the initial model. Based on the modified model, the operational temperature of the chamber wall was proposed to be less than 60 °C to suppress the desorption of Cs in the chamber wall and to sustain the stable negative ion production. In addition, it was also suggested that a slightly higher wall temperature before the operation leads to a decrease in the amount of Cs stored at the chamber wall, resulting in suppression of Cs consumption in the ion source.

Achievement of stable negative ion production with Cs-seeded for long pulse beam operation in the prototype of Cs-seeded negative ion source for JT-60SA.

Long pulse negative ion beams of 500 keV and 154 A/m2 for 118 s have been achieved for the first time, which exceeds the requirement of the JT-60SA negative ion source. In order to solve the issues of such long pulse beams, the fast cutoff system of the power supply aims to reduce the surge current and to extend the lifetime of filaments and the suppression method of excess cesium (Cs) accumulation on the plasma grid (PG) to achieve stable negative ion production. By developing the fast cutoff system using a field programmable gate array unit for the arc power supply, the cutoff time has been reduced to 1/10 that of the original system and the lifetime of the filament was extended by three times. In order to achieve stable negative ion production, incoming Cs on the PG surface has been reduced by keeping the chamber wall temperature below 40 °C. As a result, a stable beam current drift of <6% has been achieved for the 118 s duration.

The Electron Affinity as the Highest Occupied Anion Orbital Energy with a Sufficiently Accurate Approximation of the Exact Kohn-Sham Potential.

Negative ions are not accurately represented in density functional approximations (DFAs) such as (semi)local density functionals (LDA or GGA or meta-GGA). This is caused by the much too high orbital energies (not negative enough) with these DFAs compared to the exact Kohn–Sham values. Negative ions very often have positive DFA HOMO energies, hence they are unstable. These problems do not occur with the exact Kohn–Sham potential, the anion HOMO energy then being equal to minus the electron affinity. It is therefore desirable to develop sufficiently accurate approximations to the exact Kohn–Sham potential. There are further beneficial effects on the orbital shapes and the density of using a good approximation to the exact KS potential. Notably the unoccupied orbitals are not unduly diffuse, as they are in the Hartree–Fock model, with hybrid functionals, and even with (semi)local density functional approximations (LDFAs). We show that the recently developed B-GLLB-VWN approximation [Gritsenko et al. J. Chem. Phys.2016, 144, 204114] to the exact KS potential affords stable negative ions with HOMO orbital energy close to minus the electron affinity.

Negative Ion Formation in Low-Energy Electron Collisions with the Actinide Atoms Th, Pa, U, Np and Pu

Here we investigate ground and metastable negative ion formation in low-energy electron collisions with the actinide atoms Th, Pa, U, Np and Pu through the elastic total cross sections (TCSs) calculations. For these atoms, the presence of two or more open d- and f- subshell electrons presents a formidable computational task for conventional theoretical methods, making it difficult to interpret the calculated results. Our robust Regge pole methodology which embeds the crucial electron correlations and the vital core-polarization interaction is used for the calculations. These are the major physical effects mostly responsible for stable negative ion formation in low-energy electron scattering from complex heavy systems. We find that the TCSs are characterized generally by Ramsauer-Townsend minima, shape resonances and dramatically sharp resonances manifesting ground and metastable negative ion formation during the collisions. The extracted from the ground states TCSs anionic binding energies (BEs) are found to be 3.09eV, 2.98eV, 3.03eV, 3.06eV and 3.25eV for Th, Pa, U, Np and Pu, respectively. Interestingly, an additional polarization-induced metastable TCS with anionic BE value of 1.22eV is generated in Pu due to the size effect. We also found that our excited states anionic BEs for several of these atoms compare well with the existing theoretical electron affinities including those calculated using the relativistic configuration-interaction method. We conclude that the existing theoretical calculations tend to identify incorrectly the BEs of the resultant excited anionic states with the electron affinities of the investigated actinide atoms; this demonstrates the great need for experimental verification and unambiguous determination of their electron affinities.

An Occam's razor approach to chemical hardness: lex parsimoniae.

The term "chemical hardness" refers to the resistance to deformation of the electronic density of a system; the greater this resistance, the "harder" the system. Polarizability, a physical property, is an inverse measure of resistance to deformation and thus should be inversely related to hardness. This is indeed generally accepted. Hardness has been postulated to be the second derivative of a system's energy with respect to its number of electrons, despite the fact that this involves the differentiation of a noncontinuous function. This second derivative is typically approximated as the difference between the ionization energy I and the electron affinity A of the ground-state system, which results in ambiguity in that many molecules do not form stable negative ions. For atoms, the quantity I - A does vary approximately inversely with polarizability, but this is only because the electron affinity is usually relatively low and ionization energy is known to be inversely related to polarizability for atoms. However, molecular polarizability depends primarily upon volume, and so does not show an acceptable inverse correlation with I - A. Since both hardness and polarizability refer to the same property of a system-its resistance to deformation of the electronic density, we propose that the reciprocal of polarizability be taken to be a measure of hardness. We show that polarizabilities that are not known can be estimated quite accurately in terms of the average local ionization energies on the atomic or molecular surfaces and, for molecules, their volumes.

Theoretical analyses of the time-resolved nuclear dynamics of the transition state for the 1,3,5,7-cyclooctatetraene unimolecular reaction

When a stable negative ion is similar in structure to the transition state for the neutral reaction, photodetachment of the anion can be used to directly access the transition state region of the neutral potential energy surface. In this work, from the theoretical side, we address the femtosecond time-resolved experiment for the cyclooctatetraene (COT) unimolecular reaction which has been previously performed by Zewail et al. (2004), where the time-evolution of the nuclear wave packet, which is initially localized around the transition state region via instantaneous photodetachment, is monitored by an ionization laser. The oscillatory behavior of the ionization efficiency observed in their experiment is analyzed in detail using both the reduced-dimensionality quantum dynamics calculations and full-dimensional direct dynamics calculations on the CASSCF-level potential energy surfaces. We found that the behavior observed in an early stage can be attributable to the ring-inversion dynamics of COT.

Effective ionisation coefficients and critical breakdown electric field of CO2 at elevated temperature: effect of excited states and ion kinetics

Electrical breakdown by the application of an electric field occurs more easily in hot gases than in cold gases because of the extra electron-species interactions that occur as a result of dissociation, ionization and excitation at higher temperature. This paper discusses some overlooked physics and clarifies inaccuracies in the evaluation of the effective ionization coefficients and the critical reduced breakdown electric field of CO2 at elevated temperature, considering the influence of excited states and ion kinetics. The critical reduced breakdown electric field is obtained by balancing electron generation and loss mechanisms using the electron energy distribution function (EEDF) derived from the Boltzmann transport equation under the two-term approximation. The equilibrium compositions of the hot gas mixtures are determined based on Gibbs free energy minimization considering the ground states as well as vibrationally and electronically excited states as independent species, which follow a Boltzmann distribution with a fixed excitation temperature. The interaction cross sections between electrons and the excited species, not reported previously, are properly taken into account. Furthermore, the ion kinetics, including electron–ion recombination, associative electron detachment, charge transfer and ion conversion into stable negative ion clusters, are also considered. Our results indicate that the excited species lead to a greater population of high-energy electrons at higher gas temperature and this affects the Townsend rate coefficients (i.e. of electron impact ionization and attachment), but the critical reduced breakdown electric field strength of CO2 is only affected when also properly accounting for the ion kinetics. Indeed, the latter greatly influences the effective ionization coefficients and hence the critical reduced breakdown electric field at temperatures above 1500 K. The rapid increase of the dissociative electron attachment cross-section of molecular oxygen with rising vibrational quantum number leads to a larger electron loss rate and this enhances the critical reduced breakdown electric field strength in the temperature range where the concentration of molecular oxygen is relatively high. The results obtained in this work show reasonable agreement with experimental results from literature, and are important for the evaluation of the dielectric strength of CO2 in a highly reactive environment at elevated temperature.

A new look at Thomas–Fermi theory

ABSTRACTIn this short note, we argue that Thomas–Fermi theory, the simplest of all density functional theories, although failing to explain features such as molecular binding or stability of negative ions, is surprisingly accurate in estimating sizes of atoms. We give both numerical, experimental and rigorous mathematical evidence for this claim. Motivated by this, we formulate two new mathematical conjectures on the exactness of Thomas–Fermi theory.

Generation of neutral atomic beams utilizing photodetachment by high power diode laser stacks

We demonstrate the use of high power diode laser stacks to photodetach fast hydrogen and carbon anions and produce ground term neutral atomic beams. We achieve photodetachment efficiencies of ∼7.4% for H(-) at a beam energy of 10 keV and ∼3.7% for C(-) at 28 keV. The diode laser systems used here operate at 975 nm and 808 nm, respectively, and provide high continuous power levels of up to 2 kW, without the need of additional enhancements like optical cavities. The alignment of the beams is straightforward and operation at constant power levels is very stable, while maintenance is minimal. We present a dedicated photodetachment setup that is suitable to efficiently neutralize the majority of stable negative ions in the periodic table.

The use of isoprene as a novel dopant in negative ion atmospheric pressure photoionization mass spectrometry coupled to high-performance liquid chromatography.

As in the case with positive ion atmospheric pressure photoionization (PI-APPI), the addition of dopants significantly improves the sensitivity of negative ion APPI (NI-APPI). However, the research on dopant-assisted-NI-APPI has been quite limited compared to the studies on dopant-assisted PI-APPI. This work presents the potential of isoprene as a novel dopant for NI-APPI. Thirteen compounds, possessing suitable gas-phase ion energetic properties in order to make stable negative ions, were selected. Dopants were continuously introduced into a tee junction prior to the ion source through a fused-silica capillary, while analytes were directly injected into the same tee. Then both were mixed with the continuous solvent from high-performance liquid chromatography (HPLC), nebulized, and entered the source. The nebulized stream was analyzed by APPI tandem quadrupole mass spectrometry in the negative ion mode. The results obtained using isoprene were compared with those obtained by using toluene as a dopant and dopant-free NI-APPI. Isoprene enhanced the ionization intensities of the studied compounds, which were found to be comparable and, in some cases, more effective than toluene. The mechanisms leading to the observed set of negative analyte ions were also discussed. Because in NI-APPI, thermal electrons, which are produced during the photoionization of a dopant, are considered the main reagent ions, both isoprene and toluene promoted the ionization of analytes through the same mechanisms, as expected. Isoprene was shown to perform well as a novel dopant for NI-APPI. Isoprene has a high photoabsorption cross section in the VUV region; therefore, its photoionization leads to a highly effective production of thermal electrons, which further promotes the ionization of analytes. In addition, isoprene is environmentally benign and less toxic compared to currently used dopants.

Implications of odd oxygen observations by the TIMED/SABER instrument for lower D region ionospheric modeling

We document the variability in atomic oxygen inferred by the Sounding of the Atmosphere with Broadband Emission Radiometry (SABER) instrument on the NASA/TIMED satellite in the lower mesosphere (50–80km altitude) according to its diurnal, latitudinal, seasonal and solar cycle components. The dominant variation is diurnal and latitudinal. Below 75km, seasonal and solar cycle effects are less than 5%. Accordingly, we have developed a simple climatology that depends upon local time and latitude and applied it to a model of the D region of the ionosphere. Between 60 and 70km, atomic oxygen is important in governing the ratio of negative ions to electrons. Using the SABER O climatology along with a previously published climatology of nitric oxide based upon UARS/HALOE data, we compare our model results both to previous calculations and to a profile of electron density [e−] acquired by a rocket launched from Kwajalein Atoll. The model results are shown to be consistent with previously published calculations, but the comparison with the data reveals a dramatic discrepancy whereby the calculated [e−] is over an order of magnitude less than the observations below 65km. The most plausible explanation involves changing the partition of negative charge between molecules such as O2 which rapidly dissociate in sunlight versus heavier, more stable negative ions. Although observations of [e−] below 70km are difficult and infrequent, more research should be invested to evaluate the pervasiveness and the seasonal, latitudinal and diurnal morphology of this model [e−] deficit. This may have practical implications as empirical models of the ionosphere predict a secondary maximum in HF radio absorption in the 70km altitude region.

Generation of gas-phase zirconium fluoroanions by electrospray of an ionic liquid.

New approaches for forming anions are sought that have strong abundance and no isobaric overlap, attributes that are compatible with the measurement of isotope ratios. Fluoroanions are particularly attractive because fluorine is monoisotopic, and thus will not have overlapping isobars with the isotope of interest. Since many elements do not have positive electron affinity values, they do not form stable negative atomic ions, and hence are not compatible with isotope ratio measurement using high sensitivity isotope ratio mass spectrometers such as accelerator mass spectrometers. Zirconium fluoroanions were prepared using the fluorinating ionic liquid (IL) 1-ethyl-3-methylimidazolium fluorohydrogenate, which was used to generate abundant [ZrF5](-) ions using electrospray ionization. The IL was dissolved in acetonitrile, combined with a dilute solution of either Zr(4+) or ZrO(2+), and then electrosprayed. Mass analysis and collision-induced dissociation experiments were conducted using a time-of-flight mass spectrometer. Cluster structures were predicted using density functional theory calculations. The fluorohydrogenate IL solutions generated abundant [ZrF5](-) ions starting from solutions of both Zr(4+) and ZrO(2+). The mass spectra also contained IL-bearing cluster ions, whose compositions indicated the presence of [ZrF6](2-) in solution, a conclusion supported by the structural calculations. Rinsing out the zirconium-IL solution with acetonitrile decreased the IL clusters, but enhanced [ZrF5](-), which was sorbed by the polymeric electrospray supply capillary, and then released upon rinsing. This reduced the ion background in the mass spectrum. The fluorohydrogenate-IL solutions are a facile way to form zirconium fluoroanions in the gas phase using electrospray. The approach has potential as a source of fluoroanions for isotope ratio measurements, which would enable high-sensitivity measurement of minor zirconium isotopes without overlapping isobars caused by the charge carrier (i.e., the monoisotopic fluorine atoms).

A combined rocket-borne and ground-based study of the sodium layer and charged dust in the upper mesosphere

The Hotel Payload 2 rocket was launched on January 31st 2008 at 20.14 LT from the Andøya Rocket Range in northern Norway (69.31° N, 16.01° E). Measurements in the 75–105km region of atomic O, negatively-charged dust, positive ions and electrons with a suite of instruments on the payload were complemented by lidar measurements of atomic Na and temperature from the nearby ALOMAR observatory. The payload passed within 2.58km of the lidar at an altitude of 90km. A series of coupled models is used to explore the observations, leading to two significant conclusions. First, the atomic Na layer and the vertical profiles of negatively-charged dust (assumed to be meteoric smoke particles), electrons and positive ions, can be modelled using a self-consistent meteoric input flux. Second, electronic structure calculations and Rice–Ramsperger–Kassel–Markus theory are used to show that even small Fe–Mg–silicates are able to attach electrons rapidly and form stable negatively-charged particles, compared with electron attachment to O2 and O3. This explains the substantial electron depletion between 80 and 90km, where the presence of atomic O at concentrations in excess of 1010cm−3 prevents the formation of stable negative ions.

Resonant electron attachment to polar aromatic molecules: consequences for their chemistry in the interstellar medium

In this paper we present and discuss the results obtained from ab-initio quantum scattering calculations of the response from neutral aromatic species like C6H5 (phenyl) and C6H4 (benzyne, ortho isomer) to low-energy electron collisions. Our main purpose is to investigate the possible mechanisms that can lead to the final formation of their stable negative ions under astrophysical conditions, by linking low-lying metastable anionic states to bound anionic states. Quantum chemical calculations were also employed to confirm the features of the metastable resonant states found by the scattering calculations, while the role of the permanent dipole moments of both systems on the scattering behaviour for near-threshold electrons is also analysed in some detail. The possible energy redistribution paths for stabilizing both anionic species under ISM conditions are discussed in the conclusions.

Stable negative ions and shape resonances in a series of organic molecules

We report on the theoretical determination of low-lying shape resonances in a selected set of seven molecules. The finite element discrete model method is used and the absolute differences between calculated and experimental values, where known, are ≲0.15 eV for the resonances lowest in energy. Difficulties expected with the higher calculated values are discussed. This article reports results for ortho-benzyne, benzene, naphthalene, anthracene, styrene, formamide, and acetamide. Comparisons are made with a few other calculations, again where available.

CARBON-RICH MOLECULAR CHAINS IN PROTOPLANETARY AND PLANETARY ATMOSPHERES: QUANTUM MECHANISMS AND ELECTRON ATTACHMENT RATES FOR ANION FORMATION

The elementary mechanisms through which molecular polyynes could form stable negative ions after interacting with free electrons in planetary atmospheres (e.g., Titan's) are analyzed using quantum scattering calculations and quantum structure methods. The case of radical species and of nonpolar partners are analyzed via specific examples for both the C n H and HC n H series, with n values from 4 to 12. We show that attachment processes to polar radicals are dominating the anionic production and that the mediating role of dipolar scattering states is crucial to their formation. The corresponding attachment rates are presented as calculated upper limits to their likely values and are obtained down to the low temperatures of interest. The effects of the computed rates, when used in simple evolutionary models, are also investigated and presented in detail.