Ion Population Research Articles

Internal Energy Deposition in Infrared Matrix-Assisted Laser Desorption Electrospray Ionization With and Without the Use of Ice as a Matrix.

The internal energy deposited into analytes during the ionization process largely influences the extent of fragmentation, thus the appearance of the resulting mass spectrum. The internal energy distributions of a series of para-substituted benzyl pyridinium cations in liquid and solid-state generated by infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) were measured using the survival yield method, of which results were subsequently compared with conventional electrospray ionization (ESI). The comparable mean internal energy values (e.g., 1.8-1.9eV at a collision energy of 15eV) and peak widths obtained with IR-MALDESI and ESI support that IR-MALDESI are essentially a soft ionization technique where analytes do not gain considerable internal energy during the laser-induced desorption process and/or lose energy during uptake into charged electrospray droplets. An unusual fragment ion, protonated pyridine, was only found for solid IR-MALDESI at relatively high collision energies, which is presumably resulted from direct ionization of the pre-charged analytes in form of salts. Analysis of tissue with an ice layer consistently yielded ion populations with higher internal energy than its counterpart without an ice layer, likely due to a substantially enhanced number of IR absorbers with ice. Further measurements with holo-myoglobin show that IR-MALDESI-MS retains the noncovalently bound heme-protein complexes under both native-like and denaturing conditions, while complete loss of the heme group occurred in denaturing ESI-MS, showing that the softness of IR-MALDESI is equivalent or superior to ESI for biomolecules.

MMS Observations of Multiscale Hall Physics in the Magnetotail

AbstractWe present Magnetospheric Multiscale mission (MMS) observations of Hall physics in the magnetotail, which compared to dayside Hall physics is a relatively unexplored topic. The plasma consists of electrons, moderately cold ions (T∼1.5 keV) and hot ions (T∼20 keV). MMS can differentiate between the cold ion demagnetization region and hot ion demagnetization regions, which suggests that MMS was observing multiscale Hall physics. The observed Hall electric field is compared with a generalized Ohm's law, accounting for multiple ion populations. The cold ion population, despite its relatively high initial temperature, has a significant impact on the Hall electric field. These results show that multiscale Hall physics is relevant over a much larger temperature range than previously observed and is relevant for the whole magnetosphere as well as for other astrophysical plasma.

Fundamental Studies of Ion Conducting Glasses: The Combined Use of NMR and Impedance Spectroscopies to Create Models of the Conduction Energy Landscapes in Solid Electrolytes

We have developed, over years of study, new ways to combine NMR with Impedance Spectroscopy measurements of fast ion conducting glasses to examine the details of the ion conduction energy landscape that ions experience in conduction process. The NMR measurements of spin-lattice relaxation rates probe all ions whether they reside in energy wells so deep as to render them essentially immobile or in energy wells so shallow that their occupation time comparable to the diffusive time between adjacent sites. Impedance spectroscopy measurements, on the other hand, measure only those mobile ions that create a measurable current on the time scale of the measurement, typically seconds to microseconds. We have exploited these different measurements of the different sets of populations of the mobile ions to extract accurate predictions of the mobile ion potential energy landscapes in glass. We have found that a Gaussian distribution about a mean activation energy can provide an accurate description of the energy landscape for all of the mobile (and immobile) ions. In this talk, we will summarize more recent measurements we have made on both Li and Na ion conducting glasses and show how our methods can be used to develop predictions of glass compositions that will optimize the ion conductivity in glass.

Analysis of radiative gravitational modes in magnetized dusty plasma with non-thermal ion distribution

The characteristics of radiative gravitational modes in non-thermal magnetized dusty plasma with charge fluctuation and the polarization force of dust particles are investigated. The electron species are assumed to be radiative and the ions are assumed to be non-thermal. A normal mode analysis is applied to derive the general dispersion relation for radiative magnetized self-gravitating dusty plasma. Modified radiative condensation and self-gravitational instability criteria for both perpendicular and parallel modes of propagation are obtained. Analytically, it is found that the presence of a non-thermal ion population significantly modified the usual radiative condensation instability criterion, and damped the growth rate of the radiative mode. The obtained analytical results are further discussed in the numerical result section. We investigate the fact that the non-thermal ion population acts as a stabilizing source for radiative condensation instability in magnetized self-gravitating dusty plasma fluid, including the dust polarization force and charge fluctuation. The thermal conductivity with non-thermal ion distribution quickly moves the system towards stability. The implications of the results in the region of the interstellar medium (ISM) are discussed.

Heat transport driven by the ion temperature gradient and electron temperature gradient instabilities in ASDEX Upgrade H-modes

A study of the properties of the turbulence-driven ion and electron heat fluxes, is presented. Dedicated H-mode experiments taking advantage of the on-axis and off-axis possibilities of both neutral beam injection and electron cyclotron resonance heating available on the ASDEX Upgrade tokamak were carried out. The experimental results are interpreted by comparisons with gyrokinetic calculations. Ion heat transport is, as expected, driven by the ion temperature gradient (ITG) instability with the features predicted by theory: increase of the driven heat flux above a threshold in normalised gradient. In addition the main effects known to impact on the stability of the turbulence, temperature ratio and fast ions population, are exhibited by the experimental results and agree with the gyrokinetic calculations. It is known that the ITG also contributes to the electron heat flux, but that an electron instability can be required in addition when the ITG contribution does not drive the whole imposed electron heating. This situation, investigated by adding electron cyclotron heating, indicates that in the experiments presented here the electron temperature gradient instability develops.

Comment on “The Dominant Role of Energetic Ions in Solar Wind Interaction With the Moon” by Omidi et al.

AbstractOmidi et al. (2019) recently published a case study analysis of the lunar wake crossing by the ARTEMIS P2 spacecraft that occurred on 24 June 2015 by comparing P2 observations of plasma and magnetic fields in the lunar wake with a hybrid plasma model using upstream plasma conditions measured by ARTEMIS P1. As presented in Omidi et al., the ARTEMIS P2 ion moments during the lunar wake crossing show anomalously high temperatures and low velocities. This is due to both the lack of subtraction of background counts from penetrating radiation and the application of moment analysis during times when no ion flux was observed by ARTEMIS P2. Additionally, the hybrid results show large discrepancies with the ARTEMIS data, from which Omidi et al. concluded that an additional smaller population of suprathermal ions was required to accurately reproduce the ARTEMIS observations. This conclusion is at odds with previous investigations and, thus, deserves further study. Here we have used the Amitis hybrid plasma model to simulate the lunar wake with upstream plasma conditions determined from the ARTEMIS P1 reference observations, identical to those used in the Omidi et al. “Run‐0” hybrid model. We found that the Amitis hybrid model can successfully reproduce the structure of the lunar wake and the ARTEMIS P2 observations with good fidelity, without the inclusion of any additional high energy ion populations. We therefore conclude that energetic ions do not dominate the structure and behavior of the lunar wake, in contrast to the conclusions of Omidi et al.

Overcoming the insulating materials limitation in HiPIMS: Ion-assisted deposition of DLC coatings using bipolar HiPIMS

The present study aims to demonstrate that operating the HiPIMS discharge in bipolar regime (BP-HiPIMS) enables an energy-enhanced deposition process of high-quality hydrogen-free DLC thin films (high hardness, low coefficient of friction, good wear resistance, good adherence to the substrate and very low surface roughness). The structural and mechanical properties of DLC thin films deposited using the BP-HiPIMS technique were compared to those of the films prepared using a conventional HiPIMS process, under various deposition conditions. The BP-HiPIMS technique generates an energetic ion population and a substantial increase in the ion flux as compared to the conventional (monopolar) HiPIMS. This phenomenon overcomes the limitations when working with insulating or high electrical resistivity materials (both substrates and coatings), i.e. the need to accelerate the film-forming species. Energetic enhanced deposition conditions during bipolar HiPIMS facilitate the densification (up to 2.7 g/cm3) of amorphous carbon thin films which results in an increase in the film hardness (23 GPa) when depositing on Si substrates, without using substrate bias voltage, adhesion interfacial layer or substrate pre-treatment. Besides high hardness, the BP-HiPIMS process allows growing DLC coatings with good elastic strain to failure and high resistance to plastic deformation and cracking.

Interpreting observations of ion cyclotron emission from large helical device plasmas with beam-injected ion populations

Ion cyclotron emission (ICE) is detected from all large toroidal magnetically confined fusion (MCF) plasmas. It is a form of spontaneous suprathermal radiation, whose spectral peak frequencies correspond to sequential cyclotron harmonics of energetic ion species, evaluated at the emission location. In ICE phenomenology, an important parameter is the value of the ratio of energetic ion velocity to the local Alfvén speed . Here we focus on ICE measurements from heliotron-stellarator hydrogen plasmas, heated by energetic proton neutral beam injection (NBI) in the large helical device, for which takes values both larger (super-Alfvénic) and smaller (sub-Alfvénic) than unity. The collective relaxation of the NBI proton population, together with the thermal plasma, is studied using a particle-in-cell (PIC) code. This evolves the Maxwell–Lorentz system of equations for hundreds of millions of kinetic gyro-orbit-resolved ions and fluid electrons, self-consistently with the electric and magnetic fields. For LHD-relevant parameter sets, the spatiotemporal Fourier transforms of the fields yield, in the nonlinear saturated regime, good computational proxies for the observed ICE spectra in both the super-Alfvénic and sub-Alfvénic regimes for NBI protons. At early times in the PIC treatment, the computed growth rates correspond to analytical linear growth rates of the magnetoacoustic cyclotron instability (MCI), which was previously identified to underlie ICE from tokamak plasmas. The spatially localised PIC treatment does not include toroidal magnetic field geometry, nor background gradients in plasma parameters. Its success in simulating ICE spectra from both tokamak and, here, heliotron-stellarator plasmas suggests that the plasma parameters and ion energetic distribution at the emission location largely determine the ICE phenomenology. This is important for the future exploitation of ICE as a diagnostic for energetic ion populations in MCF plasmas. The capability to span the super-Alfvénic and sub-Alfvénic energetic ion regimes is a generic challenge in interpreting MCF plasma physics, and it is encouraging that this first principles computational treatment of ICE has now achieved this.

Comparing Long-duration Gamma-Ray Flares and High-energy Solar Energetic Particles

Little is known about the origin of the high-energy and sustained emission from solar Long-Duration Gamma-Ray Flares (LDGRFs), identified with the Compton Gamma Ray Observatory (CGRO), the Solar Maximum Mission (SMM), and now Fermi. Though Fermi/Large Area Space Telescope (LAT) has identified dozens of flares with LDGRF signature, the nature of this phenomenon has been a challenge to explain both due to the extreme energies and long durations. The highest-energy emission has generally been attributed to pion production from the interaction of >300 MeV protons with the ambient matter. The extended duration suggests that particle acceleration occurs over large volumes extending high in the corona, either from stochastic acceleration within large coronal loops or from back precipitation from coronal mass ejection driven shocks. It is possible to test these models by making direct comparison between the properties of the accelerated ion population producing the gamma-ray emission derived from the Fermi/LAT observations, and the characteristics of solar energetic particles (SEPs) measured by the Payload for Matter-Antimatter Exploration and Light Nuclei Astrophysics (PAMELA) spacecraft in the energy range corresponding to the pion-related emission detected with Fermi. For fourteen of these events we compare the two populations -- SEPs in space and the interacting particles at the Sun -- and discuss the implications in terms of potential sources. Our analysis shows that the two proton numbers are poorly correlated, with their ratio spanning more than five orders of magnitude, suggesting that the back precipitation of shock-acceleration particles is unlikely the source of the LDGRF emission.

Large Variations in the Composition of Ionic Liquid-Solvent Mixtures in Nanoscale Confinement.

Mixtures of an ionic liquid with an organic solvent are widely used as electrolytes in supercapacitors where they are often confined in porous electrodes with pore widths only slightly larger than the sizes of bare ions or solvent molecules. The composition of the electrolyte inside these pores, which may depend on the pore width and choice of electrolyte, can affect supercapacitor performance but remains poorly understood. Here, we perform all-atom molecular dynamics simulations of solutions of two different ionic liquids in acetonitrile under confinement between graphene sheets forming slit pores of various widths. We observe significant oscillations in the in-pore ionic liquid mole fraction with varying pore widths. Ions are excluded from very narrow pores, while for pore widths that tightly fit a single layer of ions, we observe an in-pore ionic liquid mole fraction over three times greater than that in the bulk. At slightly larger pore widths, we observe for different ionic liquids either a nearly complete exclusion of ions from the pore or a slight depletion of ions, while ion population again increases as pore width further increases. We develop an analytical model that can qualitatively predict the in-pore ionic liquid mole fraction based on the effective molar volumes and the pore wall interaction energies of each species. Our work suggests a new avenue for tuning the ionic liquid mole fraction in nanopores with potentially significant implications for designing systems involving nanoconfined liquid electrolytes such as supercapacitors where in-pore ion population can affect charging dynamics.

Operando NMR to Study the Dynamic Charging Mechanism of Activated Carbon Supercapacitor Electrodes

Supercapacitors have the potential to play an important role in high-power energy storage solutions, in particular for power quality and stability applications which require fast cycling and long lifetimes. However, their underlying charging mechanisms and the interactions between the electrodes, the ions and the solvent are not fully understood. In situ NMR techniques can measure in-pore ion populations and can thus provide unique insights into the charging mechanisms, but have so far focused on measurements at equilibrium. Since one of the key advantages of supercapacitors is their fast charging/discharging rates, it is crucial to be able to study the dynamic charging behavior that more closely represents the performance of a working device. In this work, we develop an operando NMR technique based on the synchronization between NMR and electrochemical measurements and investigate the dynamic charging mechanism of electric double layer capacitors based on activated carbon electrodes. The novel method uncovers the significance of the so-called “weakly adsorbed” ion environment, which is shown to take part in the charging process and is thought to be associated with mesopores within the carbon electrode. These findings advance our current understanding of supercapacitor charging mechanisms and the role of the 3D electrode structure, and the synchronized operando NMR method can be applied to a wide range of reversible devices.

Electric-field-induced composite color centers formation and Yb ions valence state change in spark plasma sintered Yb:YAG transparent ceramics

Transparent Yb:YAG ceramics with submicron-scale grains were fabricated through the spark-plasma-sintering of co-precipitated Yb:YAG powders without the use of any additives. Yb valence state shift and composite color center formation were investigated by visible range absorption spectra、Emission spectra and Electron Paramagnetic Resonance (EPR) measurements. The underlying mechanisms by which an applied field influences the valence state transition and composite color center formation are discussed in detail. Absorption spectra measurements of Yb:YAG ceramics consolidated by SPS at 1100–1300 °C revealed absorption bands located at 380, 487, 524, 634, 646, and 654 nm. EPR characterization and photoluminescence spectrum confirmed the presence of a Yb2+ ion population with the 4f13 ground state electronic configuration by the 589 nm luminescence under 354 nm excitation, formed by the Yb3+ ion capturing an electron to form Yb2+-F+ composite color centers. It was determined that both the shift in Yb valence state and the formation of composite color centers were caused by the electric field employed to conduct the sintering process.

Laboratory investigation of particle acceleration and magnetic field compression in collisionless colliding fast plasma flows

In many natural phenomena in space (cosmic-rays, fast winds), non-thermal ion populations are produced, with wave-particle interactions in self-induced electromagnetic turbulence being suspected to be mediators. However, the processes by which the electromagnetic energy is bestowed upon the particles is debated, and in some cases requires field compression. Here we show that laboratory experiments using high-power lasers and external strong magnetic field can be used to infer magnetic field compression in the interpenetration of two collisionless, high-velocity (0.01–0.1c) quasi-neutral plasma flows. This is evidenced through observed plasma stagnation at the flows collision point, which Particle-in-Cell (PIC) simulations suggest to be the signature of magnetic field compression into a thin layer, followed by its dislocation into magnetic vortices. Acceleration of protons from the plasma collision is observed as well. As a possible scenario, with 1D and 2D PIC simulations we consider a compression of the vortices against dense plasma remnants.

Infrared Ion Spectroscopy of Environmental Organic Mixtures: Probing the Composition of α-Pinene Secondary Organic Aerosol.

Characterizing the chemical composition of organic aerosols can elucidate aging mechanisms as well as the chemical and physical properties of the aerosol. However, the high chemical complexity and often low atmospheric abundance present a difficult analytical challenge. Milligrams or more of material may be needed for speciated spectroscopic analysis. In contrast, mass spectrometry provides a very sensitive platform but limited structural information. Here, we combine the strengths of mass spectrometry and infrared (IR) action spectroscopy to generate characteristic IR spectra of individual, mass-isolated ion populations. Soft ionization combined with in situ infrared ion spectroscopy, using the tunable free-electron laser FELIX, provides detailed information on molecular structures and functional groups. We apply this technique, along with quantum mechanical modeling, to characterize organic molecules in secondary organic aerosol (SOA) formed from the ozonolysis of α-pinene. Spectral overlap with a standard is used to identify cis-pinonic acid. We also demonstrate the characterization of isomers for multiple SOA products using both quantum mechanical computations and analyses of fragment ion spectra. These results demonstrate the detailed structural information on isolated ions obtained by combining mass spectrometry with fingerprint IR spectroscopy.

Modelling ion populations in astrophysical plasmas: carbon in the solar transition region

The aim of this work is to improve the modelling of ion populations in higher density, lower temperature astrophysical plasmas, of the type commonly found in lower solar and stellar atmospheres. Ion population models for these regions frequently employ the coronal approximation, which assumes conditions more suitable to the upper solar atmosphere, where high temperatures and lower densities prevail. The assumed conditions include all ions being in the ground state and steady-state equilibrium, where there is sufficient time for ionisation and recombination to take place. Using the coronal approximation for modelling the solar transition region gives theoretical lines intensities for the Li-like and Na-like isoelectronic sequences which are often factors of two to five times lower than observed. The works of Burgess & Summers (1969, ApJ, 157, 1007) and Nussbaumer & Storey (1975, A&A, 44, 321) show the important part ions in excited levels play when included in the modelling. As density increases metastable levels become populated and ionisation rates increase, whereas dielectronic recombination through highly excited levels is suppressed. Photo-ionisation is also shown by Nussbaumer & Storey to have an effect on the charge-state distribution of carbon in these regions. Their models, however, use approximations for the atomic rates to determine the ion balance. Presented here is the first stage in updating these earlier models of carbon by using rates from up-to-date atomic calculations and more recent photo-ionising radiances. Where atomic rates were not readily available, in the case of electron impact direct ionisation and excitation–auto-ionisation, new calculations were made using the Flexible Atomic Code and Autostructure, and compared to theoretical and experimental studies. The effects each atomic process has on the ion populations as density changes is illustrated, and final results from the modelling are compared to the earlier works. Lastly, the new results for ion populations were used to predict line intensities for the solar transition region in the quiet Sun. In comparison to coronal approximation modelling the new results show significantly improved agreement with observations.

An atomistic insight into interfacial properties of brine nanofilm confined between calcite substrate and hydrocarbon layer

Abstract Molecular dynamics simulation was applied in this study to scrutinize the interfacial properties of water nano-film confined between calcite mineral and hydrocarbon layer, as two intrinsically different media. Such system resembles the environment experienced by water molecules in the pore spaces of underground carbonate reservoirs. The interplay between water film and confining phases, oil and mineral, strongly influences hydrocarbon production process; however, there is a lack of detailed understanding of the involved interactions. MD simulations indicate development of several layers with different water densities in the confined brine. Water molecules form well-ordered structure in three hydration layers neighboring calcite substrate through particular interactions with the mineral. Likewise, the development of hydrogen bonding results in a subtle arrangement of the molecules in oil/water interface. The extent of water self-hydrogen bonding differs in each layer and is lowest in interfacial regions as a result of interruption by water-calcite (or oil) interactions. It was pointed out that strong interactions are responsible for higher residence time of water within the interfacial layers. We also studied the contribution of mono- and divalent ions (Na+, Cl−, Mg2+ and SO42−) wandering in the thin brine film. While Na+ and Cl− create a double layer over substrate, their effect on the water structuring is quite insignificant. However, the dense population of ions in interfacial regions, particularly calcite/brine, results in larger residence time of water in those regions which is a sign of a more water-wetness of the substrate.

Measurement of charge exchange between Na and Ca+ in a hybrid trap

We present measurements of the charge-exchange reaction rate between neutral sodium (Na) and ionized calcium (\ce{Ca+}) in a hybrid atom-ion trap, which is comprised of a Na magneto-optical trap concentric with a linear Paul trap. Once the Na and \ce{Ca+} are co-trapped, the reaction rate is measured by continuously quenching the reaction product \ce{Na+} from the ion trap, and then destructively measuring the decay of the remaining ion population. The reactants' electronic state and temperature are experimentally controlled, allowing us to determine the four individual reaction-rates between $\text{Na}[\text{S~or~P}]$ and $\text{Ca}^+[\text{S~or~D}]$ at different collision energies. With the exception of the largest reaction-rate channel ($\text{Na}[\text{S}]+\text{Ca}^+[\text{D}]$), our rates agree with classical Langevin rate limit. We have also found evidence of reactant collision-energy thresholds associated with two of the four entrance-channels.

Observation of accelerated beam ion population during edge localized modes in the ASDEX Upgrade tokamak

The interaction between fast-ions and edge localized modes (ELMs) is investigated by means of fast-ion loss detector measurements. Fast-ion losses are increased during ELMs exhibiting a 3D filamentary-like behaviour. An accelerated beam ion population has been observed during ELMs in a tokamak for the first time. Tomographic inversion of the measured fast-ion losses reveal multiple velocity-space structures. Attending to the experimental observations, an acceleration mechanism is proposed based on a resonant interaction between the beam ions and parallel electric fields emerging during the ELM crash. The key experimental observations can be qualitatively reproduced by full-orbit following simulations of fast-ions in the presence of the ELM magnetic and electric perturbation fields. Our findings may shed light on the possible contribution of fast-ions to the ELM stability and the transient heat loads on plasma facing components.

Ion kinetics and nonlinear saturation of current-driven instabilities relevant to hollow cathode plasmas

Ion kinetics and time evolution of bulk plasma properties in the nonlinear saturation regime of a collisionless current-driven instability are studied using a 1D Vlasov–Poisson simulation. In the simulations, the ratio of initial electron bulk velocity to initial electron thermal velocity, called the electron Mach number, ranges from 0.5 to 2.5, and electron-to-ion temperature ratio is 10. A significant population of backstreaming high-energy ions is observed when the initial electron Mach number is larger than or equal to 1.3, which agrees with previous literature indicating transition to the Buneman instability. The simulations suggest that the electrons trapped in large-amplitude waves result in a bi-directional ion acoustic wave, which generates a backward-propagating high-energy ion distribution. A concise formula that describes the high-energy ion distribution and potential fluctuation amplitude are obtained as a function of initial electron Mach numbers. Sputtering rate calculations using the non-Maxwellian distributions for ions obtained from the simulation and Maxwellian ion distributions of temperatures ranging from 0.5 to 4.0 eV are compared, illustrating the potential contribution of kinetic effects on cathode erosion.

The Dominant Role of Energetic Ions in Solar Wind Interaction With the Moon

AbstractWe use the results of 3‐D electromagnetic hybrid (kinetic ions and fluid electrons) simulations and observations by the Time History of Events and Macroscale Interactions during Substorms (THEMIS) /Acceleration, Reconnection, Turbulence and Electrodynamics of the Moon's Interaction with the Sun (ARTEMIS) spacecraft to investigate the nature of the solar wind interaction with the moon and the resulting wake and tail structure. In the absence of a global magnetic field and an atmosphere at the moon, this interaction is due to the absorption of the solar wind plasma on the dayside and the means by which the resulting cavity in the tail is refilled. To explore this process, we conducted simulations of specific case studies well‐monitored by the ARTEMIS spacecraft. Preliminary runs revealed that when the solar wind core plasma is driving the interaction, the results deviate significantly from observations. When the small population of solar wind energetic ions is incorporated in the model, the observations are reproduced much better. Simulations with different density or energy of energetic ions show considerable changes in the results indicating their dominance in establishing the electromagnetic properties of the tail. In contrast, the results show less sensitivity to the solar wind flow speed. Here we conclude that the structure of the interaction region consists of compressional and rarefaction wakes and a central tail region with areas of enhanced and possibly reduced magnetic field level. The compressional wake diverts the flow away from the tail, and its presence is found to be highly time dependent while the rarefaction wake diverts the flow toward the tail and is found to be a semipermanent feature of the lunar interaction region.