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NASA NTRS2018

Effects of Multiscale Phase-Mixing and Interior Conductance in the Lunar-like Pickup Ion Plasma Wake. First Results from 3-D Hybrid Kinetic Modeling

The study of multiscale pickup ion phase-mixing in the lunar plasma wake with a hybrid model is the main subject of our investigation in this paper. Photoionization and charge exchange of protons with the lunar exosphere are the ionization processes included in our model. The computational model includes the self-consistent dynamics of the light (hydrogen ions or hydrogen molecule ion or helium ion), and heavy (sodium ion ) pickup ions. The electrons are considered as a fluid. The lunar interior is considered as a weakly conducting body. In this paper we considered for the first time the cumulative effect of heavy neutrals in the lunar exosphere (e.g., Aluminum, Argon), an effect which was simulated with one species of sodium ion but with a tenfold increase in total production rates. We find that various species produce various types of plasma tail in the lunar plasma wake. Specifically, sodium ion and helium ion pickup ions form a cycloid-like tail, whereas the hydrogen ion or hydrogen molecule ion pickup ions form a tail with a high density core and saw-like periodic structures in the flank region. The length of these structures varies from 1:5 R(sub M) to 3:3 R(sub M) depending on the value of gyro radius for hydrogen ion or hydrogen molecule ion pickup ions. The light pickup ions produce more symmetrical jump in the density and magnetic field at the Mach cone which is mainly controlled by the conductivity of the interior, an effect previously unappreciated. Although other pickup ion species had little effect on the nature of the interaction of the Moon with the solar wind, the global structure of the lunar tail in these simulations appeared quite different when the hydrogen molecule ion production rate was high.

Lipatov, A.S.↗

NASA NTRS2018

MAVEN Case Studies of Plasma Dynamics in Low‐Altitude Crustal Magnetic Field at Mars 1: Dayside Ion Spikes Associated With Radial Crustal Magnetic Fields

We report for the first time, simultaneous ion, electron, magnetic field vector and electric field wave measurements made possible by Mars Atmosphere and Volatile EvolutioN, during ion energy flux spikes in low‐altitude radial crustal magnetic fields on the Mars dayside. Observations show energetic electrons and ions (E > 25 eV) precipitating on magnetic field lines assumed as closed. Ions (E < 1.4 keV) display broad velocity distributions toward Mars, showing ions flowing from higher altitude possibly after magnetic reconnection or loss cone filling from pitch angle scattering effects. Precipitating ions (E < 1.4 keV) show nonadiabatic features depending on ion mass and energy and returning ions (E < 1.4 keV) show evidence of conserving the first adiabatic invariant in a mirror field. We observe magnetic field perturbations up to 60 nT, electric field wave amplitudes up to 38 mV/m, and brief periods of peaked electron spectra. At ∼175 km and at times Mars Atmosphere and Volatile EvolutioN is below the mirroring altitude of electrons, we observe mirroring and transverse heating of H+ ions alongside increased electric field wave amplitude fluctuations. It suggests field aligned potential drops result from different mirror altitudes of ions and electrons. Ions E > 1.4 keV (O+) occur as injected accelerated ion beams and ions heated after energization or deceleration. Energy dispersed kilo‐electron‐volt ions suggest a selection effect in radial magnetic fields for lower‐energy Marsward ions, compared to reflection of higher‐energy anti‐Sunward ions. Precipitating kilo‐electron‐volt ions show energy deposition rates of 3.6 ×10(exp -6) W/sq m and sputtering escape rates from precipitating O+ ions of 1.5 ×10(exp 5)/(sq cm.s) and 2.1 ×10(exp 6)/(sq cm.s) are calculated.

Plasma Dynamics↗

NASA NTRS2001

Pick-Up Ion Instabilities at Planetary Magnetospheres

This effort involved the analysis of low frequency waves as observed by the Galileo spacecraft near the Galilean moon, Io. Io is a significant source of material, especially SO2, and various products of dissociation, and further these atoms and molecules are readily ionized. The initial velocity of the ions is essentially that of the neutral species, i.e., the Keplerian velocity. The plasma, on the other hand is co-rotating, and there is a differential flow of the order 57 km/s between the plasma and the neutral particles. Thus pick-up ion instabilities are Rely to occur within the Jovian magnetosphere. Indeed, magnetometer observations from the Galileo spacecraft clearly show ion cyclotron waves that have been identified with a large variety of plasma species, such as O+, S++ (which has the same gyro-frequency as O+), S+, and SO2+. Typically, however, the dominant frequency is near the SO2+ gyro-frequency. The research effort was originally planned to be a team effort between Robert J. Strangeway as the Principal Investigator, and Debbie Huddleston, who was an Assistant Research Geophysicist at UCLA. Unfortunately, Dr. Huddleston took a position within Industry. The effort was therefore descoped, and Dr. Strangeway instead pursued a collaboration with Dr. Xochitl Blanco-Cano, of the Instituto de Geofisica, Universidad Nacional Autonoma de Mexico. This has proved to be a productive collaboration, with several papers and publications arising out of the effort. The magnetic field oscillations near lo generally fall into two types: ion cyclotron waves, with frequencies near an ion gyro-frequency, and lower frequency mirror-mode waves. The ion cyclotron waves are mainly transverse, and frequently propagate along the ambient magnetic field. The mirror-mode waves are compressional waves, and they have essentially zero frequency in the plasma rest frame. One of the purposes of our investigation is to understand what controls the types of wave modes that occur, since both wave modes can be drive unstable by the pressure anisotropy associated with the pick up ions. The pick ion velocity is perpendicular to the ambient magnetic field, and is generally much larger than the thermal velocity, at least initially. At its simplest, we found that the ion cyclotron waves are controlled by the parameters of the species in gyro-resonance with the wave. Thus, while the growth rates for the lower mass (higher gyro-frequency) pick-up ions are generally larger, we found that the heavier SO2+ ion cyclotron waves are generally preferred. This is because one of the effects of the wave instability is to diffuse the ions in pitch angle and energy. The lower mass ions therefore consist of both a ring of recently created pick-up ions, and a thermal background. This thermal background quenches the ion cyclotron instability. SO2+ is different, however. Being a molecule, the species can also dissociate. Our analysis suggests that the dissociation acts on a time scale comparable to or faster than the velocity space diffusion time scale. There are consequently no thermal SO2+ ions to quench the instability. We have also investigated the mirror-mode. This mode can at times grow more rapidly than the individual ion cyclotron waves. This is mainly because the mirror-mode can grow off the pressure anisotropy of the individual species with which the waves are in resonance. Lastly, as part of this effort we have begun to investigate the instability for obliquely propagating modes. Galileo observations show that at times the ion cyclotron waves are significantly elliptically polarized, and further the wave vector is at a large angle to the field, significant growth can occur for oblique propagation. Depending on the group velocity of the waves, it is possible that obliquely propagating modes have higher advective growth rate, but this has yet to be determined.

Strangeway, Robert J.↗

NASA NTRS2010

Suppressing Loss of Ions in an Atomic Clock

An improvement has been made in the design of a compact, highly stable mercury- ion clock to suppress a loss of ions as they are transferred between the quadrupole and higher multipole ion traps. Such clocks are being developed for use aboard spacecraft for navigation and planetary radio science. The modification is also applicable to ion clocks operating on Earth: indeed, the success of the modification has been demonstrated in construction and operation of a terrestrial breadboard prototype of the compact, highly stable mercury-ion clock. Selected aspects of the breadboard prototype at different stages of development were described in previous NASA Tech Briefs articles. The following background information is reviewed from previous articles: In this clock as in some prior ion clocks, mercury ions are shuttled between two ion traps, one a 16- pole linear radio-frequency trap, while the other is a quadrupole radio-frequency trap. In the quadrupole trap, ions are tightly confined and optical state selection from a 202Hg lamp is carried out. In the 16-pole trap, the ions are more loosely confined and atomic transitions are interrogated by use of a microwave beam at approximately 40.507 GHz. The trapping of ions effectively eliminates the frequency pulling that would otherwise be caused by collisions between clock atoms and the wall of a gas cell. The shuttling of the ions between the two traps enables separation of the state-selection process from the clock microwave-resonance process, so that each of these processes can be optimized independently of the other. This is similar to the operation of an atomic beam clock, except that with ions the beam can be halted and reversed as ions are shuttled back and forth between the two traps. When the two traps are driven at the same radio frequency, the strength of confinement can be reduced near the junction between the two traps, depending upon the relative phase of the RF voltage used to operate each of the two traps, and can cause loss of ions during each transit between the traps and thereby cause loss of the 40.507-GHz ion-clock resonance signal. The essence of the modification is to drive the two traps at different frequencies typically between 1.5 and 2 MHz for the quadrupole trap and a frequency a few hundred kHz higher for the 16- pole trap. A frequency difference of a few hundred kHz ensures that the ion motion caused by the trapping electric fields is small relative to the diameter of the traps. Unlike in the case in which both traps are driven at the same frequency, the trapping electric fields near the junction are not zero at all times; instead, the regions of low electric field near the junction open and close at the difference frequency. An additional benefit of making the 16-pole trap operate at higher frequency is that the strength or depth of the multipole trap can be increased independent of the quadrupole ion trap.

Prestage, John↗

DOE OSTI2021

Fast ion transport by sawtooth instability in the presence of ICRF-NBI synergy in JET plasmas

JET experiments have shown that the three-ion scenarios using waves in the ion cyclotron range of frequencies (ICRF) is an efficient way to build fast ion population through beam ion acceleration by radio frequency (RF) waves. Here, such a heating scheme is applied to plasmas with at least two thermal ion species. Analysis of mixed discharges with complex heating schemes requires a workflow that allows to model thermal and fast ion transport consistently. This paper is dedicated to modelling of a mixed plasma discharge with significant fraction of fast ions and contributes to development of fast ion transport models. For interpretive analysis with the TRANSP code a JET hydrogen-deuterium (HD) plasma discharge with neutral beam injection (NBI) and ICRF heating has been chosen. The task is complicated by NBI-ICRF synergy and plasma magnetohydrodynamic activity, like sawtooth crashes. D beam ions accelerated by RF waves form a high energy tail in fast ion distribution. Significant difference between the neutron rate computed by TRANSP and measured one is observed if the same diffusivity for electrons and ions is assumed. Sensitivity studies show that uncertainties in input plasma parameters and thermal ion transport models are crucial for modelling mixed plasma discharges and increased D transport is required to reach the plasma composition consistent with diagnostic measurements at the plasma edge. Fast ion redistribution by a sawtooth instability is characterised by non-resonant transport due to reconnection of magnetic field lines and resonant transport caused by resonance interaction between the instability and fast ions. With ORBIT simulations it has been shown that resonant interaction strongly affects fast ions of high energies, like beam ions accelerated by RF waves and fusion products. For the considered case, fast ion profiles simulated by ORBIT remain peaked after the sawtooth crashes.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

NASA NTRS1994

Solar wind contribution to the average population of energetic He(+) and He(++) ions in the Earth's magnetosphere

Measurements with the ion charge-energy-mass spectrometer CHEM on the AMPTE/CCE spacecraft were used to investigate the origin of energetic He(+) and He(++) ions observed in the equatorial plane at 3 less than or equal to L less than or equal to 9. Special emphasis was laid on the dependence of long-term average distributions on magnetic local time (MLT) and the geomagnetic activity index K(sup p). The observations are described in terms of the phase space densities f(sub 1) (for He(+)) and f(sub 2) (for He(++)). They confirm preliminary results from a previous study f(sub 1) is independent of MLT, whereas f(sub 2) is much larger on the nightside than on the dayside. They show, furthermore, that f(sub 1) increases slightly with K(sub p) on intermediate drift shells, but decreases on high drift shells (L greater than or equal to 7). f(sub 2) increases with K(sub p) on all drift shells outside the premidnight sector. Within this sector a decrease is observed on high drift shells. A simple ion tracing code was developed to determine how and from where the ions move into the region of observations. It provides ion trajectories as a function of the ion charge, the magnetic moment and K(sub p). The ion tracing enables a distinction between regions of closed drift orbits (ring current) and open convection trajectories (plasma sheet). It also indicates how the outer part of the observation region is connected to different parts of the more distant plasma sheet. Observations and tracing show that He(++) ions are effectively transported from the plasma sheet on convection trajectories. Their distribution in the observation region corresponds to the distribution of solar wind ions in the plasma sheet. Thus, energetic He(++) ions most likely originate in the solar wind. On the other hand, the plasma sheet is not an important source of energetic He(+) ions. Convection trajectories more likely constitute a sink for He(+) ions, which may diffuse onto them from closed drift orbits and then get lost through the magnetopause. An ionospheric origin of energetic He(+) ions is unlikely as well, since the source mechanism should be almost independent of K(sub p). There is considerable doubt, however, that a plausible mechanism also exists during quiet periods that can accelerate ions to ring current energies, while extracting them from the ionosphere. It is concluded, therefore, that energetic He(+) ions are mainly produced by charge exchange processes from He(++) ions. This means that most of the energetic He(+) ions constituting the average distributions also very likely originate in the solar wind. Additional ionospheric contributions are possible during disturbed periods.

Kremser, G.↗

NASA NTRS1989

Simulations and Observations of Heating of Auroral Ion Beams

In the auroral zone, quasi-static parallel electric fields produce beams of ionospheric ions (e.g., H(+), He(+) and 0(+)), which flow outward into the magnetosphere, providing a significant source of ions for the ring current and plasma sheet. Because the velocities to which these beams are accelerated is dependent on the mass of the ions, differential flows between the various ion species can develop which are unstable to an ion-ion streaming instability. Particle simulations and observations from DE 1 are used to investigate the heating of the ion beams produced by this instability. It is shown that there is net transfer of energy from the light ions to the heavy ions, with the heavy ions reaching maximum velocities near the beam velocity of the light ions. Bulk heating of the heavy ions occurs when their relative density is low while high-energy tails are produced when their relative density is high. The heating is primarily parallel to the magnetic field if the difference in the heavy and light ion beam velocities is subsonic while both perpendicular and parallel heating can occur if it is supersonic. In the latter case, very strong heating of an intermediate ion's species such as He(+) can also occur. Comparison with observations shows features consistent with heating via the ion-ion instability including perpendicular heating in the supersonic regime and parallel heating in the subsonic regime and a change in the heating between these regimes as the ratio of the H(+) beam speed to the local sound speed is observed to decrease. This heating is, however, not always observed in association with enhanced wave emissions. This lack of waves is attributed to reabsorption of the waves as the ions become heated.

Winglee, R. M.↗

NASA NTRS1997

Multi-Species Test of Ion Cyclotron Resonance Heating at High Altitudes

Observations of ion distributions and plasma waves obtained by the Dynamics Explorer 1 satellite in the high-altitude, nightside auroral zone are used to study ion energization for three ion species. A number of theoretical models have been proposed to account for the transverse heating of these ion populations. One of these, the ion cyclotron resonance heating (ICRH) mechanism, explains ion conic formation through ion cyclotron resonance with broadband electromagnetic wave turbulence in the vicinity of the characteristic ion cyclotron frequency. The cyclotron resonant heating of the ions by low- frequency electromagnetic waves is an important energy source for the transport of ions from the ionosphere to the magnetosphere. In this paper we test the applicability of the ICRH mechanism to three simultaneously heated and accelerated ion species by modelling the ion conic formation in terms of a resonant wave-particle interaction in which the ions extract energy from the portion of the broadband electromagnetic wave spectrum which includes the ion cyclotron frequency. Using a Monte Carlo technique we evaluate the ion heating produced by the electromagnetic turbulence at low frequencies and find that the wave amplitudes near the ion cyclotron frequencies are sufficient to explain the observed ion energies.

Persoon, A. M.↗

NASA NTRS1997

Multi-Species Test of Ion Cyclotron Resonance Heating at High Altitudes

Observations of ion distributions and plasma waves obtained by the Dynamics Explorer 1 satellite in the high-altitude, nightside auroral zone are used to study ion energization for three ion species. A number of theoretical models have been proposed to account for the transverse heating of these ion populations. One of these, the ion cyclotron resonance heating (ICRH) mechanism, explains ion conic formation through ion cyclotron resonance with broadband electromagnetic wave turbulence in the vicinity of the characteristic ion cyclotron frequency. The cyclotron resonant heating of the ions by low-frequency electromagnetic waves is an important energy source for the transport of ions from the ionosphere to the magnetosphere. In this paper we test the applicability of the ICRH mechanism to three simultaneously heated and accelerated ion species by modelling the ion conic formation in terms of a resonant wave-particle interaction in which the ions extract energy from the portion of the broadband electromagnetic wave spectrum which includes the ion cyclotron frequency. Using a Monte Carlo technique we evaluate the ion heating produced by the electromagnetic turbulence at low frequencies and find that the wave amplitudes near the ion cyclotron frequencies are sufficient to explain the observed ion energies.

Persoon, A. M.↗

NASA NTRS2011

Evaluation of Pulse Counting for the Mars Organic Mass Analyzer (MOMA) Ion Trap Detection Scheme

The Mars Organic Mass Analyzer is being developed at Goddard Space Flight Center to identify organics and possible biological compounds on Mars. In the process of characterizing mass spectrometer size, weight, and power consumption, the use of pulse counting was considered for ion detection. Pulse counting has advantages over analog-mode amplification of the electron multiplier signal. Some advantages are reduced size of electronic components, low power consumption, ability to remotely characterize detector performance, and avoidance of analog circuit noise. The use of pulse counting as a detection method with ion trap instruments is relatively rare. However, with the recent development of high performance electrical components, this detection method is quite suitable and can demonstrate significant advantages over analog methods. Methods A prototype quadrupole ion trap mass spectrometer with an internal electron ionization source was used as a test setup to develop and evaluate the pulse-counting method. The anode signal from the electron multiplier was preamplified. The an1plified signal was fed into a fast comparator for pulse-level discrimination. The output of the comparator was fed directly into a Xilinx FPGA development board. Verilog HDL software was written to bin the counts at user-selectable intervals. This system was able to count pulses at rates in the GHz range. The stored ion count nun1ber per bin was transferred to custom ion trap control software. Pulse-counting mass spectra were compared with mass spectra obtained using the standard analog-mode ion detection. Prelin1inary Data Preliminary mass spectra have been obtained for both analog mode and pulse-counting mode under several sets of instrument operating conditions. Comparison of the spectra revealed better peak shapes for pulse-counting mode. Noise levels are as good as, or better than, analog-mode detection noise levels. To artificially force ion pile-up conditions, the ion trap was overfilled and ions were ejected at very high scan rates. Pile-up of ions was not significant for the ion trap under investigation even though the ions are ejected in so-called 'ion-micro packets'. It was found that pulse counting mode had higher dynamic range than analog mode, and that the first amplification stage in analog mode can distort mass peaks. The inherent speed of the pulse counting method also proved to be beneficial to ion trap operation and ion ejection characterization. Very high scan rates were possible with pulse counting since the digital circuitry response time is so much smaller than with the analog method. Careful investigation of the pulse-counting data also allowed observation of the applied resonant ejection frequency during mass analysis. Ejection of ion micro packets could be clearly observed in the binned data. A second oscillation frequency, much lower than the secular frequency, was also observed. Such an effect was earlier attributed to the oscillation of the total plasma cloud in the ion trap. While the components used to implement pulse counting are quite advanced, due to their prevalence in consumer electronics, the cost of this detection system is no more than that of an analog mode system. Total pulse-counting detection system electronics cost is under $250

Van Amerom, Friso H.↗

DOE OSTI2019

Transition from ion-coupled to electron-only reconnection: Basic physics and implications for plasma turbulence

Here using 2.5 dimensional kinetic particle-in-cell simulations, we simulate reconnection conditions appropriate for the magnetosheath and solar wind, i.e., plasma beta (ratio of gas pressure to magnetic pressure) greater than 1 and low magnetic shear (strong guide field). Changing the simulation domain size, we find that the ion response varies greatly. For reconnecting regions with scales comparable to the ion inertial length, the ions do not respond to the reconnection dynamics leading to “electron-only” reconnection with very large quasisteady reconnection rates. Note that in these simulations, the ion Larmor radius is comparable to the ion inertial length. Moreover, the transition to a more traditional “ion-coupled” reconnection is gradual as the reconnection domain size increases, with the ions becoming frozen-in in the exhaust when the magnetic island width in the normal direction reaches many ion inertial lengths. During this transition, the quasisteady reconnection rate decreases until the ions are fully coupled, ultimately reaching an asymptotic value. The scaling of the ion outflow velocity with the exhaust width during this electron-only to ion-coupled transition is found to be consistent with a theoretical model of a newly reconnected field line. In order to have a fully frozen-in ion exhaust with ion flows comparable to the reconnection Alfvén speed, an exhaust width of at least several ion inertial lengths is needed. In turbulent systems with reconnection occurring between magnetic bubbles associated with fluctuations, using geometric arguments, we estimate that fully ion-coupled reconnection requires magnetic bubble length scales of at least several tens of ion inertial lengths.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2024

Curious cross-field transport effects in multi-ion, magnetized plasma

In contrast to single-ion plasma, multiple-ion-species plasma exhibits new, curious, and large transport effects. On short timescales, where ions exchange momentum, magnetized multi-ion plasma behaves as a most unusual substance, compressible across field lines in number density but incompressible in charge density. It takes 40 times longer for electrons to participate. In this ion–ion cross-field transport regime, we identified the charge-incompressibility heat pump effect, transferring heat both spatially and between species. Curiously, the direction of impurity transport strongly depends on plasma magnetization, characterized by the ratio of light ion gyrofrequency to the collision frequency between light and heavy ion species. The expulsion of heavy ion impurities from a hotspot occurs sufficiently quickly to be observable on MagLIF, so long as plasma becomes sufficiently collisionally magnetized under implosion. Even more curious, multi-ion transport changes its nature in partially ionized plasma, where ions occupy different charge states. In this regime, we identify a partial-ionization deconfinement effect. The combination of cross-field transport, ionization, and recombination leads to a net ion charge moving across magnetic field lines on the ion–ion transport timescale as opposed to the electron–ion transport timescale. Cross-field transport effects in multi-ion plasma are important in a number of applications, including nuclear fusion and plasma mass filters.

Mlodik, M. E. (ORCID:0000000343003941)↗

NASA NTRS1999

Low-Energy Sputtering Studies of Boron Nitride with Xenon Ions

Sputtering of boron nitride with xenon ions was investigated using secondary ion (SIMS) and secondary neutral (SNMS) mass spectrometry. The ions generated from the ion gun were incident on the target at an angle of 50' with respect to the surface'normal. The energy of ions ranged from 100 eV to 3 keV. A flood electron gun was used to neutralize the positive charge build-up on the target surface. The intensities of sputtered neutral and charged particles, including single atoms, molecules, and clusters, were measured as a function of ion energy. Positive SIMS spectra were dominated by the two boron isotopes whereas BN- and B- were the two major constituents of the negative SIMS spectra. Nitrogen could be detected only in the SNMS spectra. The intensity-energy curves of the sputtered particles were similar in shape. The knees in P-SIMS and SNMS intensity-energy curves appear at around I keV which is significantly higher that 100 to 200 eV energy range at which knees appear in the sputtering of medium and heavy elements by ions of argon and xenon. This difference in the position of the sputter yield knee between boron nitride and heavier targets is due to the reduced ion energy differences. The isotopic composition of secondary ions of boron were measured by bombarding boron nitride with xenon ions at energies ranging from 100 eV to 1.5 keV using a quadrupole mass spectrometer. An ion gun was used to generate the ion beam. A flood electron gun was used to neutralize the positive charge buildup on the target surface. The secondary ion flux was found to be enriched in heavy isotopes at lower incident ion energies. The heavy isotope enrichment was observed to decrease with increasing primary ion energy. Beyond 350 eV, light isotopes were sputtered preferentially with the enrichment increasing to an asymptotic value of 1.27 at 1.5 keV. The trend is similar to that of the isotopic enrichment observed earlier when copper was sputtered with xenon ions in the same energy range.

Ray, P. K.↗

DOE OSTI2019

Determination of Gas-Phase Ion Mobility Coefficients Using Voltage Sweep Multiplexing

In a standard single averaged, drift tube ion mobility spectrometry (IMS) experiment, typically less than 1% of the ions are utilized, with the rest of the ions neutralizing on a closed ion gate or ion optic element. Though some efforts at lower pressures (e.g., 4 Torr) have been made to address this issue by concentrating ions prior to release into a drift cell, the ion current reaching the detector during an IMS experiment is often diminished due to this lower duty cycle. Additionally, when considering the temporal nature of the drift tube IMS experiment and the trajectory of IMS towards higher resolution separations and lower duty cycles, increased detector sampling rates are another factor also which further necessitates new modes of conducting the IMS experiment. Placing this trend in context with ion mobility-mass spectrometry instruments (IM-MS), there are numerous types of mass spectrometers that are simply incompatible with the single averaged ion mobility spectrometry experiments due to timing incompatibilities (i.e., ion traps are an order of magnitude slower than the IMS experiment). However, by utilizing a dual gate ion mobility spectrometer for ion multiplexing, ion utilization efficiency can be significantly increased while creating a measurement signal that can be recorded at low sampling rates. In this work, we present the fundamental theory and first results from proof-of-concept measurements using a new type of ion multiplexing that relies on changing the electric field within the drift cell during the course of an experiment while simultaneously opening the ion gates at a constant frequency. For brevity, this mode is termed voltage sweep multiplexing (VSM). Key variables for this type of experiment are discussed and verified with measurements from traditional signal averaged experiments. .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2019

SLIM Ultrahigh Resolution Ion Mobility Spectrometry Separations of Isotopologues and Isotopomers Reveal Mobility Shifts due to Mass Distribution Changes

We report on separations of ion isotopologues and isotopomers using ultrahigh-resolution traveling wave-based Structures for Lossless Ion Manipulations with serpentine ultralong path and extended routing ion mobility spectrometry coupled to mass spectrometry (SLIM SUPER IMS-MS). Mobility separations of ions from the naturally occurring ion isotopic envelopes (e.g., [M], [M+1], [M+2]…ions) showed the first and second isotopic peaks (i.e. [M+1] and [M+2]) for various tetraalkylammonium ions could be resolved from their respective monoisotopic ion peak ([M]) after SLIM SUPER IMS with resolving powers of ~400-600. Similar separations were obtained for other compounds (e.g., tetrapeptide ions). Greater separation was obtained using argon versus helium drift gas, as expected from the greater reduced mass contribution to ion mobility described by the Mason-Schamp relationship. To more directly explore the role of isotopic substitutions, we studied a mixture of specific isotopically substituted (15N, 13C, and 2H) protonated arginine isotopologues. While the separations in nitrogen were primarily due to their reduced mass differences, similar to the naturally occurring isotopologues, their separations in helium, where higher resolving powers could also be achieved, revealed distinct additional relative mobility shifts. These shifts appeared correlated, after correction for the reduced mass contribution, with changes in the ion center of mass due to the different locations of heavy atom substitutions. The origin of these apparent mass distribution- induced mobility shifts was then further explored using a mixture of Iodoacetyl Tandem Mass Tag (iodoTMT) isotopomers (i.e. each having the same exact mass, but with different isotopic substitution sites). Again, the observed mobility shifts appeared correlated with changes in the ion center of mass leading to multiple monoisotopic mobilities being observed for some isotopomers (up to a ~0.04% difference in mobility). These mobility shifts thus appear to reflect details of the ion structure, derived from the changes due to ion rotation impacting collision frequency or momentum transfer, and highlight the potential for new approaches for ion structural characterization.

Isotopologues, isotopomers, SLIM, Ion Mobility Spe↗

DOE OSTI2018

Enhanced Ion Adsorption on Mineral Nanoparticles

Classical molecular dynamics simulation was used to study the adsorption of Na + , Ca 2+ , Ba 2+ and Cl-ions on gibbsite edge (1 0 0), basal (0 0 1), and nanoparticle surfaces. The gibbsite nanoparticle consists of both basal and edge surfaces. Simulation results indicate that Na + and Cl - ions adsorb on both (1 0 0) and (0 0 1) surfaces as inner-sphere species (i.e., no water molecules between an ion and the surface). Outer-sphere Cl - ions (i.e., one water molecule between an ion and the surface) were also found on these surfaces. On the (1 0 0) edge, Ca 2+ ions adsorb as inner-sphere and outer-sphere complexes, while on the (0 0 1) surface outer-sphere Ca 2+ ions are the dominant species. Ba 2+ ions were found as inner-sphere and outer-sphere complexes on both surfaces. Calculated ion surface coverages indicate that, for all ions, surface coverages are always higher on the basal surface compared to the edge surface. More importantly, surface coverages for cations on the gibbsite nanoparticle are always higher than those calculated for (1 0 0) and (0 0 1) surfaces. This enhanced ion adsorption behavior for the nanoparticle is due to the significant number of inner-sphere cations found at nanoparticle corners. Outer-sphere cations do not contribute to the enhanced surface coverage. In addition, there is no ion adsorption enhancement observed for the Cl - ion. Our work provides a molecular-scale understanding of the relative significance of ion adsorption onto gibbsite basal versus edge surfaces and demonstrates the corner effect on ion adsorption on nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Photoluminescence, thermoluminescence and defect centres in Y2O3 and Y2O3:Tb3+ under 100 MeV swift Ni8+ ion beam irradiation

Highlights: • XRD showed decrease of crystallite size after ion irradiated. • Electron spin resonance reveals the presence of F, F{sup +} and O{sub 2}{sup −} centres. • SHI irradiated Y{sub 2}O{sub 3}:Tb{sup 3+} exhibits purity of intense green emission and long life time. • The Tb{sup 3+} doped Y{sub 2}O{sub 3} shows a linear, greater TL efficiency, longer life time and less fading under SHI irradiation. - Abstract: Y{sub 2}O{sub 3} and Y{sub 2}O{sub 3}:Tb{sup 3+} powders, synthesized via the solution combustion method, were studied in order to determine the effect of 100 MeV swift Ni{sup 8+} ions on the photoluminescence (PL), thermoluminescence (TL) and swift ion beam induced defects. Synthesized materials were characterized by X-ray powder diffraction, electron spin resonance, PL intensity, decay measurements and TL. Cubic structures were observed in both the pristine and ion irradiated materials. The ion irradiated materials exhibited smaller crystallite sizes than that of the pristine material. PL peaks in the visible region were identified at 485, 542, 582 and 621 nm due to the {sup 5}D{sub 4}→{sup 7}F{sub 3,4,5,6} transition of Tb{sup 3+}. The PL intensity showed an increase up to 3 × 10{sup 10} ions cm{sup −2} and then a significant decrease with a further increase in the ion fluence. The recorded time resolved PL at an ion irradiated fluence of 3 × 10{sup 10} ions cm{sup −2}, exhibited an increase in the life time of the material. TL glow curves were obtained for the samples irradiated with a swift Ni{sup 8+} ion beam. These glow curves showed a peak at 518 K with a shoulder peak at 473 K and its intensity linearly increased upto a fluence of 1 × 10{sup 11} ions cm{sup −2}. Whereas, the undoped sample showed peaks at 421 and 662 K and its intensity sub-linearly increased upto a fluence of 1 × 10{sup 11} ions {sup −2}. TL efficiency values of the Y{sub 2}O{sub 3}:Tb{sup 3+} sample, irradiated by a 100 MeV Ni{sup 8+} ion beam, have been measured relative to the undoped Y{sub 2}O{sub 3} sample and were found to be 1.34. The Tb{sup 3+} doped sample exhibited a less fading effect under the swift heavy ion beam.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2020

Erratum to: Soft- and reactive landing of ions onto surfaces: concepts and applications

Soft- and reactive landing of mass-selected ions is gaining attention as a promising approach for the precisely-controlled preparation of materials on surfaces that are not amenable to deposition using conventional methods. A broad range of ionization sources and mass filters are available that make ion soft-landing a versatile tool for surface modification using beams of hyperthermal (<100?eV) ions. The ability to select the mass-to-charge ratio of the ion, its kinetic energy and charge state, along with precise control of the size, shape, and position of the ion beam on the deposition target distinguishes ion soft landing from other surface modification techniques. Soft- and reactive landing have been used to prepare interfaces for practical applications as well as precisely-defined model surfaces for fundamental investigations in chemistry, physics, and materials science. For instance, soft- and reactive landing have been applied to study the surface chemistry of ions isolated in the gas-phase, prepare arrays of proteins for high-throughput biological screening, produce novel carbon-based and polymer materials, enrich the secondary structure of peptides and the chirality of organic molecules, immobilize electrochemically-active proteins and organometallics on electrodes, create thin films of complex molecules, and immobilize catalytically active organometallics as well as ligated metal clusters. In addition, soft landing has enabled investigation of the size-dependent behavior of bare metal clusters in the critical subnanometer size regime where chemical and physical properties do not scale predictably with size. The morphology, aggregation, and immobilization of larger bare metal nanoparticles, which are directly relevant to the design of catalysts as well as improved memory and electronic devices, have also been studied using ion soft landing. This review article begins in section 1 with a brief introduction to the existing applications of ion soft- and reactive landing. Section 2 provides an overview of the ionization sources and mass filters that have been used to date for soft landing of mass-selected ions. A discussion of the competing processes that occur during ion deposition as well as the types of ions and surfaces that have been investigated follows in section 3. Section 4 discusses the physical phenomena that occur during and after ion soft landing, including retention and reduction of ionic charge along with factors that impact the efficiency of ion deposition. The influence of soft landing on the secondary structure and biological activity of complex ions is addressed in section 5. Lastly, an overview of the structure and mobility as well as the catalytic, optical, magnetic, and redox properties of bare ionic clusters and nanoparticles deposited onto surfaces is presented in section 6. © 2015 Wiley Periodicals, Inc. Mass Spec Rev 35:439–479, 2016.

Johnson, Grant E.↗