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At least 19 records

Resonance ionization mass spectrometry for isotopic abundance measurements

Resonance ionization mass spectrometry (RIMS) is a relatively new laser-based technique for the determination of isotopic abundances. The resonance ionization process depends upon the stepwise absorption of photons from the laser, promoting atoms of the element of interest through progressively higher electronic states until an ion is formed. Sensitivity arises from the efficiency of the resonant absorption process when coupled with the power available from commercial laser sources. Selectivity derives naturally from the distinct electronic structure of different elements. This isobaric discrimination has provided the major impetus for development of the technique. Resonance ionization mass spectrometry was used for analysis of the isotopic abundances of the rare earth lutetium. Isobaric interferences from ytterbium severely effect the ability to measure small amounts of the neutron-deficient Lu isotopes by conventional mass spectrometric techniques. Resonance ionization for lutetium is performed using a continuous-wave laser operating at 452 nm, through a sequential two-photon process, with one photon exciting the intermediate resonance and the second photon causing ionization. Ion yields for microgram-sized quantities of lutetium lie between 10(6) and 10(7) ions per second, at overall ionization efficiencies approaching 10(-4). Discrimination factors against ytterbium greater than 10(6) have been measured. Resonance ionization for technetium is also being explored, again in response to an isobaric interference, molybdenum. Because of the relatively high ionization potential for Tc, three-photon, two-color RIMS processes are being developed.

Miller, C. M.↗

Three-color resonance ionization spectroscopy of Zr in Si

As our society becomes technologically more complex, computers are being used in greater and greater numbers of high consequence systems. Giving a machine control over the lives of humans can be disturbing, especially if the software that is run on such a machine has bugs. Formal reasoning is one of the most powerful techniques available to demonstrate the correctness of a piece of software. When reasoning about software and its development, one frequently encounters expressions that contain partial functions. As might be expected, the presence of partial functions introduces an additional dimension of difficulty to the reasoning framework. This difficulty produces an especially strong impact in the case of high consequence systems. An ability to use formal methods for constructing software is essential if we want to obtain greater confidence in such systems through formal reasoning. This is only reasonable under automation of software development and verification. However, the ubiquitous presence of partial functions prevents a uniform application to software of any tools not specifically accounting for partial functions. In this paper we will describe a framework for reasoning about software, based on the nonstrict explicit domain approach, that is applicable to a large class of software/hardware systems. In this framework the Hoare triples containing partial functions can be reasoned about automatically in a well-defined and uniform manner.

Hansen, C. S.↗

Modeling of the initiation and evolution of a laser-ionized column in the lower atmosphere - 314.5 nm wavelength resonant multiphoton ionization of naturally occurring argon

A 3+1 resonant multiphoton ionization process in naturally occurring argon is studied at 314.5 nm as a candidate for providing a long ionized channel through the atmosphere. Results are presented which indicate peak electron densities up to 10 exp 8/cu cm can be created using laser intensities on the order of 10 exp 8 W/sq cm.

Fetzer, G. J.↗

New electronic states of NH and ND observed by resonance enhanced multiphoton ionization spectroscopy

Resonance Enhanced MultiPhoton Ionization (REMPI) spectra of NH and ND, which reveal four new electronic states are presented. Transitions from NH a 1 delta to 3s and 3p Rydberg states in both NH and ND have been observed and rotationally analyzed. The transitions were observed in the wavelength range of 258 to 288 nm. The state assignments are: e 1 pi (3s sigma) at 82857/cm, f 1 pi (3p sigma) at 86378/cm, g 1 delta (3p pi) at 88141/cm and h 1 sigma (3p pi) at 89151/cm.

Johnson, Russell D., III↗

Experimental investigation of Stark broadening and plasma polarization shift of ionized helium resonance lines

Stark broadening and shift measurements were performed on ionized helium resonance lines from a fully ionized helium plasma in a low-inductance electromagnetic T tube. Both time-integrated photographic and time-resolved photoelectric measurements of the lines were performed with a grazing incidence spectrometer. Electron density and temperature were determined from the widths of the He II 4686-A and the He I 5876-A lines and the He II 4686-A line to continuum ratio, respectively. It was found that all ionized helium resonance lines were emitted optically thick by a homogeneous plasma slab and self-reversed by a thin cooler boundary layer. Marked blue shifts of 0.07 plus or minus 0.05 A which may be due to plasma polarization were noted.

Neiger, M.↗

Resonant enhanced multiphoton ionization studies of atomic oxygen

In resonant enhanced multiphoton ionization (REMPI), an atom absorbs several photons making a transition to a resonant intermediate state and subsequently ionizing out of it. With currently available tunable narrow-band lasers, the extreme sensitivity of REMPI to the specific arrangement of levels can be used to selectively probe minute amounts of a single species (atom) in a host of background material. Determination of the number density of atoms from the observed REMPI signal requires a knowledge of the multiphoton ionization cross sections. The REMPI of atomic oxygen was investigated through various excitation schemes that are feasible with available light sources. Using quantum defect theory (QDT) to estimate the various atomic parameters, the REMPI dynamics in atomic oxygen were studied incorporating the effects of saturation and a.c. Stark shifts. Results are presented for REMPI probabilities for excitation through various 2p(3) (4S sup o) np(3)P and 2p(3) (4S sup o) nf(3)F levels.

Dixit, S. N.↗

Experimental Resonance Enhanced Multiphoton Ionization (REMPI) studies of small molecules

Resonance enhanced multiphoton ionization (REMPI) utilizes tunable dye lasers to ionize an atom or molecule by first preparing an excited state by multiphoton absorption and then ionizing that state before it can decay. This process is highly selective with respect to both the initial and resonant intermediate states of the target, and it can be extremely sensitive. In addition, the products of the REMPI process can be detected as needed by analyzing the resulting electrons, ions, fluorescence, or by additional REMPI. This points to a number of exciting opportunities for both basic and applied science. On the applied side, REMPI has great potential as an ultrasensitive, highly selective detector for trace, reactive, or transient species. On the basic side, REMPI affords an unprecedented means of exploring excited state physics and chemistry at the quantum-state-specific level. An overview of current studies of excited molecular states is given to illustrate the principles and prospects of REMPI.

Dehmer, J. L.↗

A study of a high resolution IUE spectrum of AM Canum Venaticorum

We have obtained the first high resolution IUE spectrum of the helium-rich, cataclysmic variable star AM CVn. The spectrum is greatly underexposed, but we can still detect both wide and narrow line profiles. We report broad, shortward-shifted, P-Cygni-like absorption and in some cases emission lines in the far UV high ionization resonance lines of C, N, O, and Si, but the profiles are considerably disk/boundary layer outflows, absorption disk continuum light in H-rich CVs. The highest ionizations show evidence of a narrow jet or conical flow. For other, lower ionized lines, we find some evidence of a stellar origin. The broad He II (lambda 1640 A) absorption profile with blue shifted emission core has a remarkably similar overall structure to the He II (lambda 1640 A) broad absorption trough in the IUE spectrum of the prototypical cool DO white dwarf HZ 21. The sharp absorption lines seem most convincingly in the resonance doublets of N V (lambda 1238 A, lambda 1242 A) and C IV (lambda 1548 A, lambda 1550 A) and in He II (lambda 1640 A) exhibit a precise velocity coincidence. These sharp features are almost certainly due to circumbinary matter because they are obviously unaffected by the rapid orbital motion (or rapid stellar rotation) in this short period system during the long (9.3 hour) IUE echelle exposure. Our observations support an evolution through shell episodes of a close binary system which ends up with an expanding envelope as seen for HZ 21, and suggests one possible evolutionary channel for production of DOs (DBs).

Solheim, J.-E.↗

Evidence for a warm wind from the red star in symbiotic binaries

A systematic redshift of the high ionization resonance emission lines with respect to the intercombination lines is found from an examination of the ultraviolet spectra of symbiotic stars obtained with IUE. After consideration of other possibilities, this is most probably explained by photon scattering in an expanding envelope optically thick to the resonance lines. Line formation in a wind, or at the base of a wind is therefore suggested. Reasons are also given indicating line formation of the most ionized species in a region with an electron temperature of the order of 100,000 K, probably around the cool star. The behavior of the emission line width with ionization energy seems to support this model. The cool components of symbiotic stars appear to differ from normal red giants, which do not have winds of this temperature. An explanation in terms of a higher rotation velocity due to the binary nature of these stars is suggested.

Friedjung, M.↗

Quantitative determination of H2, HD, and D2 internal-state distributions by (2+1) resonance-enhanced multiphoton ionization

Results are presented of an experimental study of (2+1) resonance-enhanced multiphoton ionization (REMPI) detection of H2, HD, and D2 via the E,F two-photon transition, in which the relationship between ion signals and quantum-state populations was determined by calibration against a thermal effusive source. Vibrational and rotational correction factors were obtained for 102 rovibrational levels for v-double-prime = 0, 1, and 2 and for J-double-prime ranging from 0 to 17. These correction factors make it possible to convert ion signals into relative quantum-state populations without relying on a theoretical description of the (2+1) REMPI process.

Rinnen, Klaus-Dieter↗

A search for evidence of past and ongoing mass loss in the hot DO degenerates PG 1159 - 035, PG 1034 + 001, and KPD 0005 + 5106

The results are reported of a search for evidence of mass loss from three very hot, helium-rich degenerate stars, PG 1034 + 001, PG 1159 - 035, and KPD 0005 + 5106, based upon a search for weak, velocity-displaced line features in high-resolution IUE spectra. The search was entirely negative for PG 1159 - 035 and resulted in the detection of Si IV in PG 1034 + 001 at the same redshifted velocity as the other detected far-ultraviolet resonance doublets. The presence of photospheric silicon in a DO star at 80,000 K is not predicted by current radiative acceleration theory. For KPD 0005 + 5106 there is no convincing far-ultraviolet spectroscopic detection of either past or ongoing mass loss. The high-ionization resonance doublets of C IV, Si IV, and N v share the same velocity broadening as the interstellar lines but are velocity displaced by + 10 km/s relative to the local interstellar medium. Their origin is ascribed to an expanding, photoionized H II region around KPD 0005 + 5106.

Fritz, Matthew L.↗

Miniature Mass Spectrometers on Space and Planetary Missions

Space flight mass spectrometers contribute our understanding of the origin and evolution of our solar system and even of life itself. This fundamental role has motivated increasing interest in miniature mass spectrometry for planetary missions. Several remarkable new instruments are en route or under development to investigate the composition of planetary bodies such as Mars and comets. For instance, the Sample Analysis at Mars (SAM) suite on the 2009 Mars Science Laboratory (MSL) mission includes a quadrupole mass spectrometer with a sophisticated gas processing system as well as pyrolysis and chemical derivatization protocols for solid samples. Future missions will require even lighter, lower power, and yet more capable mass spectrometers, particularly to analyze samples in situ on planetary surfaces. We have been developing laser-based mass spectrometers for elemental and organic/molecular analysis of rock, ice, or fine particle samples. These typically use time-of-flight (TOF) mass analyzers, which are readily miniaturized and can detect both atomic species and complex organics that occur in a variety of planetary materials. For example, nonvolatile polycyclic aromatic hydrocarbons and kerogen-like macromolecular carbon are found in some carbonaceous meteorites, which derived from asteroid parent bodies. A single focused laser pulse is able to volatilize and ionize some of these compounds for direct TOF analysis. While this is possible without any sample preparation or contact, sensitivity and quantitative performance can improve significantly with some sample handling. As such we have also been examining robotic mechanisms and protocols to accompany space flight mass spectrometers. In addition, sensors in early development may significantly improve these capabilities, via use of techniques such as switchable polarity, ambient pressure, or resonant ionization; tandem mass spectrometry (TOF or ion trap); and chemical imaging.

Brinckerhoff, William↗