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At least 19 records

Spin contamination in unrestricted Hartree-Fock calculations.

Several pi-electron doublets are treated by both the unrestricted Hartree-Fock method and the restricted approximation of Longuet-Higgins and Pople. For two of the molecules, which contain oxygen heteroatoms, serious spin contamination occurs in the UHF wavefunctions, and this negates the usefulness of the single annihilation procedure that is often used for spin-density calculations. The restricted approximation provides a convenient alternative, especially because configuration interaction is easily taken into account.

Schug, J. C.↗

The approximate second order coupled-cluster method based on a size-consistent Brillouin–Wigner partitioning

We present a variant of the approximate second order coupled-cluster method (CC2) with a two-parameter size-consistent Brillouin–Wigner (BW-s) partitioning instead of a Møller–Plesset (MP) partitioning for the unperturbed Hamiltonian, which we refer to as BWs-CC2. The computational complexity of this model scales identically to CC2 with molecular size. Conventional CC2 and its regularized BWs-CC2 variants, as well as conventional MP2 and two of its regularized BW-s2 variants, were assessed on a 535 element database spanning thermochemistry, non-covalent interactions, barrier heights, and isomerization energies. To ensure a well-defined model chemistry, the assessment was performed using internally stable spin-polarized Hartree–Fock (HF) orbitals in the finite aug-cc-pVQZ basis without counterpoise corrections. As a result of using stable orbitals, contrary to conventional wisdom, we find that CC2 substantially outperforms MP2 on molecules with significantly spin contaminated reference orbitals without a significant increase in error on systems with a spin-pure reference, showing the value of its single substitutions. While no single choice of regularization parameters can be optimal for all datasets, we find that BWs-CC2 generally outperforms both CC2 and BW-s2 with a single judicious parameter choice. Additional tests on dipole moments and bond lengths of diatomics provide further support for the utility of this choice. Furthermore, the main outliers and poorest performing cases are associated with large amounts of spin-contamination in the HF reference, which is indicative of systems with either strong correlation or extensive artificial symmetry breaking. Overall, these findings argue that the perception of the quality of the CC2 ground state should be reevaluated and that it can be further improved upon by the soundly based BWs-CC2 variant with the recommended parameter choice.

Correlation energy↗

Computation of the expectation value of the spin operator S^ 2 for the spin-flip Bethe–Salpeter equation

Spin-flip (SF) methods applied to excited-state approaches like the Bethe–Salpeter equation allow access to the excitation energies of open-shell systems, such as molecules and defects in solids. The eigenstates of these solutions, however, are generally not eigenstates of the spin operator S^ 2 . Even for simple cases where the excitation vector is expected to be, for example, a triplet state, the value of S^ 2 may be found to differ from 2.00; this difference is called 'spin contamination'. The expectation values S^ 2 must be computed for each excitation vector, to assist with the characterization of the particular excitation and to determine the amount of spin contamination of the state. Here, our aim is to provide for the first time in the SF methods literature a comprehensive resource on the derivation of the formulas for S^ 2 as well as its computational implementation. After a brief discussion of the theory of the SF Bethe–Salpeter equation (BSE) and some examples further illustrating the need for calculating S^ 2 , we present the derivation for the general equation for computing S^ 2 with the eigenvectors from an SF-BSE calculation, how it is implemented in a Python script, and timing information on how this calculation scales with the size of the SF-BSE Hamiltonian.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Gold-Standard Chemical Database 137 (GSCDB137): A Diverse Set of Accurate Energy Differences for Assessing and Developing Density Functionals

We present GSCDB137, a rigorously curated benchmark library of 137 data sets (8377 entries) covering main-group and transition-metal reaction energies and barrier heights, (intra- and intermolecular) noncovalent interactions, dipole moments, polarizabilities, electric-field response energies, and vibrational frequencies. Legacy data from GMTKN55 and MGCDB84 have been updated to today's best reference values; redundant or low-quality points were removed, and many new, property-focused sets were added. Testing 29 popular density functional approximations (DFAs) confirms the expected Jacob's-ladder hierarchy overall but also reveals notable exceptions: functional performance for frequencies and electric-field properties correlates poorly with that for other ground-state energetics. ωB97M-V and ωB97X-V are the most balanced hybrid meta-GGA and hybrid GGA, respectively; B97M-V and revPBE-D4 lead the meta-GGA and GGA classes. Double hybrids lower mean errors by about 30% versus their hybrid analogues but demand careful frozen-core, basis set, and spin contamination treatment. GSCDB137 offers a comprehensive, openly documented platform for rigorous validation of DFA and universal machine learning potentials, and training of the next generation of exchange-correlation functionals.

Liang, Jiashu [University of California, Berkeley,↗

Recent Advances in Open-Shell Perturbation Theory and Coupled-Cluster Theory

Comparisons of various recently developed open-shell RHF perturbation theories will be presented. Among the aspects considered are spin-contamination, computational cost, and quality of numerical results. In addition, a new approach to avoid the disk storage and I/O bottlenecks in large scale coupled-cluster calculations will be discussed.

Lee, Timothy J.↗

Galileo spin rate control

This paper presents the analysis and design of the spin rate control flight algorithm for the dual-spin Galileo spacecraft. Because of thruster plume contamination constraints, only one poorly located thruster is available for spin rate correction in each spin direction. Hence, firing of any of the spin thrusters has a deleterious effect on spacecraft pointing. A control strategy was developed for achieving the desired spin rate correction while keeping disturbances at acceptable levels. This involved symmetrically distributed multiple thruster burns. Results of extensive tests of the adopted scheme on a computer simulation of the spacecraft are also presented.

Eke, F. O.↗

Genesis Ultrapure Water Megasonic Wafer Spin Cleaner

A device removes, with high precision, the majority of surface particle contamination greater than 1-micron-diameter in size from ultrapure semiconductor wafer materials containing implanted solar wind samples returned by NASA's Genesis mission. This cleaning device uses a 1.5-liter/minute flowing stream of heated ultrapure water (UPW) with 1- MHz oscillating megasonic pulse energy focused at 3 to 5 mm away from the wafer surface spinning at 1,000 to 10,000 RPM, depending on sample size. The surface particle contamination is removed by three processes: flowing UPW, megasonic cavitations, and centripetal force from the spinning wafer. The device can also dry the wafer fragment after UPW/megasonic cleaning by continuing to spin the wafer in the cleaning chamber, which is purged with flowing ultrapure nitrogen gas at 65 psi (.448 kPa). The cleaner also uses three types of vacuum chucks that can accommodate all Genesis-flown array fragments in any dimensional shape between 3 and 100 mm in diameter. A sample vacuum chuck, and the manufactured UPW/megasonic nozzle holder, replace the human deficiencies by maintaining a consistent distance between the nozzle and wafer surface as well as allowing for longer cleaning time. The 3- to 5-mm critical distance is important for the ability to remove particles by megasonic cavitations. The increased UPW sonication time and exposure to heated UPW improve the removal of 1- to 5-micron-sized particles.

Allton, Judith H.↗

Probing intrinsic magnetization dynamics of the Y 3⁢ Fe 5 ⁢O 12 /Bi 2 ⁢Te 3 interface at low temperature

Topological insulator–magnetic insulator (TI–MI) heterostructures hold significant promise in the field of spintronics, offering the potential for manipulating magnetization through topological surface state–enabled spin-orbit torque. However, many TI–MI interfaces are plagued by issues such as contamination within the magnetic insulator layer and the presence of a low-density transitional region of the topological insulator. These interfacial challenges often obscure the intrinsic behavior of the TI–MI system. In this study, we addressed these challenges by depositing sputtered Bi 2 ⁢Te 3 on liquid phase epitaxy grown Y 3 ⁢Fe 5 ⁢O 12 /Gd 3 ⁢Ga 5 ⁢O 12 . The liquid phase epitaxy grown Y 3 ⁢Fe 5 ⁢O 12 has been previously shown to have exceptional interface quality, without an extended transient layer derived from interdiffusion processes of the substrate or impurity ions, thereby eliminating rare-earth impurity-related losses in the MI at low temperatures. At the TI–MI interface, high-resolution depth-sensitive polarized neutron reflectometry confirmed the absence of a low-density transitional growth region of the TI. By overcoming these undesirable interfacial effects, we isolate and probe the intrinsic low-temperature magnetization dynamics and transport properties of the TI–MI interface. In conclusion, our findings revealed strong spin pumping at low temperatures, accompanied by an additional in-plane anisotropy. The enhanced spin pumping at low temperatures is correlated with the observed suppression of bulk conduction and the weak antilocalization in the TI film, highlighting the interplay between the transport and spin pumping behavior in the TI–MI system.

36 MATERIALS SCIENCE↗

Maneuver Design and Calibration for the Genesis Spacecraft

Genesis is the fifth mission selected as part of NASA's Discovery Program. The objective of Genesis is to collect solar wind samples for a period of approximately two years while in a halo orbit about the Earth-Sun L I point. At the end of this period, the samples are to be returned to a specific recovery point on the Earth for subsequent analysis. This goal has never been attempted before and presents a formidable challenge in terms of mission design and operations, particularly planning and execution of propulsive maneuvers. To achieve a level of cost-effectiveness consistent with a Discovery-class mission, the Genesis spacecraft design was adapted to the maximum extent possible from designs used on earlier missions, such as Mars Global Surveyor (MGS) and Stardust, another sample collection mission. The spacecraft design for Genesis is shown. Spin stabilization was chosen for attitude control, in lieu of three-axis stabilization, with neither reaction wheels nor accelerometers included. This precludes closed-loop control of propulsive maneuvers and implies that any attitude changes, including spin changes and precessions, will behave like translational propulsive maneuvers and affect the spacecraft trajectory. Moreover, to minimize contamination risk to the samples collected, all thrusters were placed on the side opposite the sample collection canister. The orientation and characteristics of thrusters are indicated. For large maneuvers (>2.5 m/s), two 5 lbf thrusters will be used for delta v, with precession to the burn attitude, followed by spin-up from 1.6 to 10 rpm before the burn and spin down to 1.6 rpm afterwards, then precession back to the original spin attitude. For small maneuvers (<2.5 m/s), no spin change is needed and four 0.2 lbf thrusters are used for Av. Single or double 360 deg. precession changes are required whenever the desired delta v falls inside the two-way turn circle (about 0.4 m/s) based on the mass properties, spin rate and lever arm lengths based on thruster locations. In such instances, delta v resulting from spacecraft precession cannot be used effectively as a component of the desired delta v, and must therefore be removed by precessing at least one complete revolution around the turn circle. To eliminate cross-track execution errors, a second revolution in the opposite direction would also be performed. This paper will address the design of propulsive maneuvers in light of the aforementioned challenges and other constraints. Maneuver design will be performed jointly by the Navigation Team at JPL and the Spacecraft Team at LMA, based on the process indicated . Typical maneuver timelines will be presented which address considerations introduced by attitude changes. These include nutation, which is introduced by precessing or spinning down and must be given sufficient time to damp out prior to execution of subsequent events, as well as sun and earth pointing constraints, which must be considered to ensure sufficient spacecraft power and to minimize telecommunications interruptions, respectively. The paper will include a description of how individual propulsive maneuvers are resolved into components to account for delta v from translational burns and spacecraft attitude changes required to carry out such maneuvers. Contributions to maneuver delta v arising from attitude changes, based on mass properties for the period just after launch, are indicated. Similar curves will be presented spanning all mission phases from launch through return. A set of closed-form equations for resolving maneuver components, base on a specific delta v required for correction or deterministic changes to the spacecraft trajectory will be presented, as well. In addition to nominal maneuvers, special calibration maneuvers are planned to improve open-loop modeling of maneuvers and to reduce execution errors. Uncalibrated execution errors are indicated. Such errors could be reduced by 50% or more over the course of the mission. Special calibrations are of particular importance for the return leg of the mission, since the sample canister must be returned to a specific location within the Utah Test and Training Range (UTTR) for mid-air retrieval. An entry angle tolerance of no less than +/- 0.08 deg. is required to achieve this objective. Biasing of the final return maneuvers coupled with a specific maneuver mode to use a series of well-characterized spin changes to effect these maneuvers is part of the current Genesis baseline mission plan. Another important objective of calibrations is to better characterize precession maneuvers. Such maneuvers are part of most propulsive maneuvers, but are also required periodically to maintain sun-pointing for power or daily during solar-wind pointing during collection periods. Although relatively small, such maneuvers will have a significant cumulative impact on orbit determination, particularly in the halo portion of the mission. The current mission design also calls for three stationkeeping maneuvers during each halo orbit of approximately six months duration. These stationkeeping maneuvers may be sufficiently small that single or double 360 deg. precession changes may be required. Because there are no accelerometers on board the spacecraft, calibration can only be performed with the aid of ground-based radiometric tracking. To establish a high degree of accuracy in characterizing the magnitude of burns, the spacecraft spin axis should be along the line of sight to the Earth, providing Doppler measurements with <1 mm/sec accuracy in S-Band. Emission constraints allow such alignment only during certain portions of the mission when the Earth-spacecraft-sun geometry is favorable. The impact of precessions, or burns at times when geometry is not favorable, can be assessed by reconstruction of the spacecraft trajectory using tracking arcs of several days before and after the event.

Williams, Kenneth E.↗

Genesis Solar Wind Collector Cleaning Assessment: Update on 60336 Sample Case Study

To maximize the scientific return of Genesis Solar Wind return mission it is necessary to characterize and remove a crash-derived particle and thin film surface contamination. A small subset of Genesis mission collector fragments are being subjected to extensive study via various techniques. Here we present an update on the sample 60336, a Czochralski silicon (Si-CZ) based wafer from the bulk array (B/C). This sample has undergone multiple cleaning steps (see the table below): UPW spin wash, aggressive chemical cleanings (including aqua regia, hot xylene and RCA1), as well as optical and chemical (EDS, ToF-SIMS) imaging. Contamination appeared on the surface of 60336 after the initial 2007 UPW cleaning. Aqua regia and hot xylene treatment (8/13/2013) did little to remove contaminants. The sample was UPW cleaned for the third time and imaged (9/16/13). The UPW removed the dark stains that were visible on the sample. However, some features, like "the Flounder" (a large, 100 micron feature in Fig. 1b) appeared largely intact, resisting all previous cleaning efforts. These features were likely from mobilized adhesive, derived from the Post-It notes used to stabilize samples for transport from Utah after the hard landing. To remove this contamination, an RCA step 1 organic cleaning (RCA1) was employed. Although we are still uncertain on the nature of the Flounder and why it is resistant to UPW and aqua regia/hot xylene treatment, we have found RCA1 to be suitable for its removal. It is likely that the glue from sticky pads used during collector recovery may have been a source for resistant organic contamination [9]; however [8] shows that UPW reaction with crash-derived organic contamination does not make particle removal more difficult.

Goreva, Y. S.↗

Influence of probe contamination on recombination of atomic hydrogen

Atomic hydrogen concentration profiles were measured through a screen-stabilized one-dimensional propane/oxygen front using a specially modified electron spin resonance (ESR) spectrometer. The ESR line occurring at 3075.5 G at 9261.2 MHz was monitored in the presence and absence of various halogenated hydrocarbons. A significant cumulative decrease in peak intensity occurred with addition of any halogenated compound. Further results suggest that the effect is due to inhibitor action on the transport tube walls followed by changes in atomic hydrogen interaction with the walls, and that hydrogen decay is nonlinear in the halogenated tube.

Collins, L. W.↗

First Year Wilkinson Microwave Anisotropy Probe (WMAP) Observations: Foreground Emission

The WMAP mission has mapped the full sky to determine the geometry, content, and evolution of the universe. Full sky maps are made in five microwave frequency bands to separate the temperature anisotropy of the cosmic microwave background (CMB) from foreground emission, including diffuse Galactic emission and Galactic and extragalactic point sources. We define masks that excise regions of high foreground emission, so CMB analyses can became out with minimal foreground contamination. We also present maps and spectra of the individual emission components, leading to an improved understanding of Galactic astrophysical processes. The effectiveness of template fits to remove foreground emission from the WMAP data is also examined. These efforts result in a CMB map with minimal contamination and a demonstration that the WMAP CMB power spectrum is insensitive to residual foreground emission. We use a Maximum Entropy Method to construct a model of the Galactic emission components. The observed total Galactic emission matches the model to less than 1% and the individual model components are accurate to a few percent. We find that the Milky Way resembles other normal spiral galaxies between 408 MHz and 23 GHz, with a synchrotron spectral index that is flattest (beta(sub s) approx. -2.5) near star-forming regions, especially in the plane, and steepest (beta(sub s) approx. -3) in the halo. This is consistent with a picture of relativistic cosmic ray electron generation in star-forming regions and diffusion and convection within the plane. The significant synchrotron index steepening out of the plane suggests a diffusion process in which the halo electrons are trapped in the Galactic potential long enough to suffer synchrotron and inverse Compton energy losses and hence a spectral steepening. The synchrotron index is steeper in the WMAP bands than in lower frequency radio surveys, with a spectral break near 20 GHz to beta(sub s) less than -3. The modeled thermal dust spectral index is also steep in the WMAP bands, with beta(sub d) approx. = 2.2. Our model is driven to these conclusions by the low level of total foreground contamination at approx. 60 GHz. Microwave and Ha measurements of the ionized gas agree well with one another at about the expected levels. Spinning dust emission is limited to less than 5% of the Ka-band foreground emission. A catalog of 208 point sources is presented. The reliability of the catalog is 98%, i.e., we expect five of the 208 sources to be statistically spurious. The mean spectral index of the point sources is alpha approx. 0(beta approx. -2). Derived source counts suggest a contribution to the anisotropy power from unresolved sources of (15.0 +/- 1.4) x 10(exp -3)micro sq K sr at Q-band and negligible levels at V-band and W-band. The Sunyaev-Zeldovich effect is shown to be a negligible "contamination" to the maps.

Bennett, C. L.↗

Containerless processing at high temperatures using acoustic levitation

Advanced techniques are presented which facilitate the development of inert or reducing atmospheres in excess of 2000 K in order to improve processing of containerless capabilities at higher temperatures and to provide more contamination-free environments. Recent testing, in the laboratory and aboard the NASA KC-135 aircraft, of a high-temperature acoustic positioner demonstrated the effectiveness of a specimen motion damping system and of specimen spin control. It is found that stable positioning can be achieved under ambient and heated conditions, including the transient states of heat-up and cool-down. An incorporated high-temperature levitator was found capable of processing specimens of up to 6-mm diameter in a high-purity environment without the contaminating effects of a container at high temperatures and with relative quiescence.

Rey, C. A.↗

Evaluation of Space Power Materials Flown on the Passive Optical Sample Assembly

Evaluating the performance of materials on the exterior of spacecraft is of continuing interest, particularly in anticipation of those applications that will require a long duration in low Earth orbit. The Passive Optical Sample Assembly (POSA) experiment flown on the exterior of Mir as a risk mitigation experiment for the International Space Station was designed to better understand the interaction of materials with the low Earth orbit environment and to better understand the potential contamination threats that may be present in the vicinity of spacecraft. Deterioration in the optical performance of candidate space power materials due to the low Earth orbit environment, the contamination environment, or both, must be evaluated in order to propose measures to mitigate such deterioration. The thirty two samples of space power materials studied here include solar array blanket materials such as polyimide Kapton H and SiO(x) coated polyimide Kapton H, front surface aluminized sapphire, solar dynamic concentrator materials such as silver on spin coated polyimide and aluminum on spin coated polyimide, CV 1144 silicone, and the thermal control paint Z-93-P. The physical and optical properties that were evaluated prior to and after the POSA flight include mass, total, diffuse, and specular reflectance, solar absorptance, and infrared emittance. Additional post flight evaluation included scanning electron microscopy to observe surface features caused by the low Earth orbit environment and the contamination environment, and variable angle spectroscopic ellipsometry to identify contaminant type and thickness. This paper summarizes the results of pre- and post-flight measurements, identifies the mechanisms responsible for optical properties deterioration, and suggests improvements for the durability of materials in future missions.

Jaworske, Donald A.↗

Five-Year Wilkinson Microwave Anisotropy Probe (WMAP1) Observations: Galactic Foreground Emission

We present a new estimate of foreground emission in the WMAP data, using a Markov chain Monte Carlo (MCMC) method. The new technique delivers maps of each foreground component for a variety of foreground models, error estimates of the uncertainty of each foreground component, and provides an overall goodness-of-fit measurement. The resulting foreground maps are in broad agreement with those from previous techniques used both within the collaboration and by other authors. We find that for WMAP data, a simple model with power-law synchrotron, free-free, and thermal dust components fits 90% of the sky with a reduced X(sup 2) (sub v) of 1.14. However, the model does not work well inside the Galactic plane. The addition of either synchrotron steepening or a modified spinning dust model improves the fit. This component may account for up to 14% of the total flux at Ka-band (33 GHz). We find no evidence for foreground contamination of the CMB temperature map in the 85% of the sky used for cosmological analysis.

Gold, B.↗

Decontaminating Solar Wind Samples with the Genesis Ultra-Pure Water Megasonic Wafer Spin Cleaner

The Genesis sample return capsule, though broken during the landing impact, contained most of the shattered ultra-pure solar wind collectors comprised of silicon and other semiconductor wafers materials. Post-flight analysis revealed that all wafer fragments were littered with surface particle contamination from spacecraft debris as well as soil from the impact site. This particulate contamination interferes with some analyses of solar wind. In early 2005, the Genesis science team decided to investigate methods for removing the surface particle contamination prior to solar wind analysis.

Calaway, Michael J.↗

Changes in the X-Ray Emission from the Magnetar Candidate 1E 2259+586 During its 2002 Outburst

An outburst of more than 80 individual bursts, similar to those seen from Soft Gamma Repeaters (SGRs), was detected from the anomalous X-ray pulsar (AXP) 1E 2259+586 in 2002 June. Coincident with this burst activity were gross changes in the pulsed flux, persistent flux, energy spectrum, pulse profile, and spin-down of the underlying X-ray source. We present Rossi X-Ray Timing Explorer and X-Ray Multi-Mirror Mission observations of 1E 2259+586 that show the evolution of the aforementioned source parameters during and following this episode and identify recovery timescales for each. Specifically, we observe an X-ray flux increase (pulsed and phase-averaged) by more than an order of magnitude having two distinct components. The first component is linked to the burst activity and decays within approx. 2 days, during which the energy spectrum is considerably harder than during the quiescent state of the source. The second component decays over the year following the glitch according to a power law in time with an exponent -0.22 +/- 0.01. The pulsed fraction decreased initially to approx. 15% rms but recovered rapidly to the preoutburst level of approx. 23% within the first 3 days. The pulse profile changed significantly during the outburst and recovered almost fully within 2 months of the outburst. A glitch of size Delta(sib (nu)max) = (4.24 +/- 0.11) x 10(exp -6) was observed in 1E 2259+586, which preceded the observed burst activity. The glitch could not be well fitted with a simple partial exponential recovery. An exponential rise of approx. 20% of the frequency jump with a timescale of approx. 14 days results in a significantly better fit to the data; however, contamination from a systematic drift in the phase of the pulse profile cannot be excluded. A fraction of the glitch (approx. 19%) was recovered in a quasi-exponential manner having a recovery timescale of approx. 16 days. The long-term postglitch spin-down rate decreased in magnitude relative to the preglitch value. The changes in the source properties of 1E 2259+586 during its 2002 outburst are shown to be qualitatively similar to changes seen during or following burst activity in two SGRs, thus further solidifying the common nature of SGRs and AXP's as magnetars. The changes in persistent emission properties of 1E 2259+586 suggest that the star underwent a plastic deformation of the crust that simultaneously impacted the superfluid interior (crustal and possibly core superfluid) and the magnetosphere. Finally, the changes in persistent emission properties coincident with burst activity in 1E 2259+586 enabled us to infer previous burst-active episodes from this and other AXP's. The nondetection of these outbursts by all-sky gamma-ray instruments suggests that the number of active magnetar candidates in our Galaxy is larger than previously thought.

Woods, P. M.↗

Thermal ion perturbations observed in the vicinity of the Space Shuttle

Thermal ion characteristics in the vicinity of the Space Shuttle, derived from RF spectrometer measurements of the Plasma Diagnostic Package (PDP) flown aboard Spacelab 2, are discussed. During the Reaction Control System firings, short pulses of enhanced ion fluxes of NO(+), O2(+), and H2O(+) were detected in the near wake within and in near proximity to the open payload. During the release of the PDP as a free flying satellite, the spin modulation of the ion fluxes in the ion spectrometer indicated the presence of plasma streams of O(+) and H2O(+) which were separated in direction by as much as 77 deg. It is concluded that the presence of contaminant NO and O2(+) ions makes the near environment of the Shuttle an unsuitable place for obtaining accurate ambient ion concentration measurements.

Grebowsky, J. M.↗