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At least 451 records · Page 25

Determining the Molecular Growth Mechanisms of Protein Crystal faces by Atomic Force Microscopy

A high resolution atomic force microscopy (AFM) study had shown that the molecular packing on the tetragonal lysozyme (110) face corresponded to only one of two possible packing arrangements, suggesting that growth layers on this face were of bimolecular height (Li et al., 1998). Theoretical analyses of the packing had also indicated that growth of this face should proceed by the addition of growth units of at least tetramer size corresponding to the 43 helices in the crystal. In this study an AFM linescan technique was devised to measure the dimensions of individual growth units on protein crystal faces. The growth process of tetragonal lysozyme crystals was slowed down by employing very low supersaturations. As a result images of individual growth events on the (110) face were observed, shown by jump discontinuities in the growth step in the linescan images. The growth unit dimension in the scanned direction was obtained by suitably averaging these images. A large number of scans in two directions on the (110) face were performed and the distribution of lysozyme aggregate sizes were obtained. A variety of growth units, all of which were 43 helical lysozyme aggregates, were shown to participate in the growth process with a 43 tetramer being the minimum observed size. This technique represents a new application for AFM allowing time resolved studies of molecular process to be carried out.

Li, Huayu↗

Novel Nanolaminates for Aerospace Applications

Nanolaminate manufacturing (NLM) is a new way of developing materials whose properties can far exceed those of homogeneous materials. Traditional alloys, composites and bulk laminates tend to average the properties of the materials from which they were made. With nanostructured materials, the high density of interfaces between dissimilar materials results in novel material properties. For example, materials made -from alternating nanoscale layers of metals and oxides have exhibited thermal conductivities far below those of the oxides themselves. Also, metallic nanolaminates can have peak strengths 100 times lager than the bulk constituent metals. Recent work at MSFC has focused on the development of nickel/aluminum oxide (Ni/Al2O3)) nanolaminates. Ni/Al2O3 nanolaminates are expected to have better strength, creep and fatigue resistance, oxygen compatibility, and corrosion resistance than the traditional metal-matrix composites of this material, which has been used in a variety of aerospace applications. A chemical vapor deposition (CW) system has been developed and optimized for the deposition of nanolaminates. Nanolaminates with layer thicknesses between 10 and 300 nm have been successfully grown and characterization has included scanning electron microscopy (SEM) and atomic force microscopy (AFM) Nanolaminates have a large variety of potential applications. They can be tailored to have both very small and anisotropic thermal conductivities and are promising as thermal coatings for both rock$ engine components and aerobraking structures. They also have the potential to be used in aerospace applications where strength at high temperatures, corrosion resistance or resistance to hydrogen embrittlement is important. Both CVD and magnetron sputtering facilities are available for the deposition of nanolayered materials. Characterization equipment includes SEM, AFM, X-ray diffraction, transmission electron microscopy, optical profilometry, and mechanical tensile pull testing.

Volz, Martin↗

1,2-Dichlorohexafluoro-Cyclobutane (1,2-c-C4F6Cl2, R-316c) a Potent Ozone Depleting Substance and Greenhouse Gas: Atmospheric Loss Processes, Lifetimes, and Ozone Depletion and Global Warming Potentials for the (E) and (Z) stereoisomers

The atmospheric processing of (E)- and (Z)-1,2-dichlorohexafluorocyclobutane (1,2-c-C4F6Cl2, R-316c) was examined in this work as the ozone depleting (ODP) and global warming (GWP) potentials of this proposed replacement compound are presently unknown. The predominant atmospheric loss processes and infrared absorption spectra of the R-316c isomers were measured to provide a basis to evaluate their atmospheric lifetimes and, thus, ODPs and GWPs. UV absorption spectra were measured between 184.95 to 230 nm at temperatures between 214 and 296 K and a parametrization for use in atmospheric modeling is presented. The Cl atom quantum yield in the 193 nm photolysis of R- 316c was measured to be 1.90 +/- 0.27. Hexafluorocyclobutene (c-C4F6) was determined to be a photolysis co-product with molar yields of 0.7 and 1.0 (+/-10%) for (E)- and (Z)-R-316c, respectively. The 296 K total rate coefficient for the O(1D) + R-316c reaction, i.e., O(1D) loss, was measured to be (1.56 +/- 0.11) × 10(exp −10)cu cm/ molecule/s and the reactive rate coefficient, i.e., R-316c loss, was measured to be (1.36 +/- 0.20) × 10(exp −10)cu cm/molecule/s corresponding to a approx. 88% reactive yield. Rate coefficient upper-limits for the OH and O3 reaction with R-316c were determined to be <2.3 × 10(exp −17) and <2.0 × 10(exp −22)cu cm/molecule/s, respectively, at 296 K. The quoted uncertainty limits are 2(sigma) and include estimated systematic errors. Local and global annually averaged lifetimes for the (E)- and (Z)-R-316c isomers were calculated using a 2-D atmospheric model to be 74.6 +/- 3 and 114.1 +/-10 years, respectively, where the estimated uncertainties are due solely to the uncertainty in the UV absorption spectra. Stratospheric photolysis is the predominant atmospheric loss process for both isomers with the O(1D) reaction making a minor, approx. 2% for the (E) isomer and 7% for the (Z) isomer, contribution to the total atmospheric loss. Ozone depletion potentials for (E)- and (Z)-R-316c were calculated using the 2-D model to be 0.46 and 0.54, respectively. Infrared absorption spectra for (E)- and (Z)-R-316c were measured at 296 K and used to estimate their radiative efficiencies (REs) and GWPs; 100-year time-horizon GWPs of 4160 and 5400 were obtained for (E)- and (Z)-R-316c, respectively. Both isomers of R-316c are shown in this work to be long-lived ozone depleting substances and potent greenhouse gases.

UV cross section↗

Evaluation of single-footprint AIRS CH4 Profile Retrieval Uncertainties Using Aircraft Profile Measurements

We evaluate the uncertainties of methane optimal estimation retrievals from single footprint thermal infrared observations from the Atmospheric Infrared Sounder (AIRS). These retrievals are primarily sensitive to atmospheric methane in the mid-troposphere through the lower stratosphere (~2 to ~17 km). We compare to in situ observations made from aircraft during the Hiaper Pole to Pole Observations (HIPPO), the NASA Atmospheric Tomography Mission (ATom) campaigns, and from the NOAA ESRL aircraft network, between the surface and 5-13 km, across a range of years, latitudes between 60 S to 80 N, and over land and ocean. After a global, pressure dependent bias correction, we find that the land and ocean have similar biases and that the reported observation error (combined measurement and interference errors) of ~27 ppb is consistent with the standard deviation between aircraft and individual AIRS observations. A single measurement has measurement (noise related) uncertainty of ~17 ppb, a ~20 ppb uncertainty from radiative interferences (e.g. from water, temperature, etc.), and ~ 30 ppb due to “smoothing error”, which is partially removed when making comparisons to in situ measurements or models in a way that account for this regularization. We estimate a 16 ppb validation error because the aircraft typically did not measure methane at altitudes where the AIRS measurements have some sensitivity, e.g. the stratosphere. Daily averaged AIRS measurements of at least 9 observations over spatio-temporal domains of < 1 degree and 1 hour have a standard deviation of ~17 ppb versus aircraft, likely because the observation errors from temperature and water vapor (for example) are only partly reduced through averaging. Seasonal averages can reduce this ~17 ppb uncertainty further to ~10 ppb, as determined through comparison with NOAA aircraft, likely because uncertainties related to radiative effects of temperature and water vapor can be reduced when averaged over a season.

Susan Kulawik↗

Variability of (O I) 6300-A emission near Io

Observations of (O I) 6300-A emission near Io have been obtained in 1990, 1991, and 1992 by the National Solar Observatory staff using the solar-stellar spectrography on the McMath-Pierce telescope at Kitt Peak. High-resolution spectra with a resolving power of about 1.2 x 10(exp 5) were obtained with an integration time of 10-15 min each. The viewing aperture for the observations was 5.2 arc sec x 5.2 arc sec centered on Io, with spatial resolution limited within this area by seeing conditions. Observations thus far have been reduced to obtain average brightness values over the aperture which range from approximately 200 to 1000 R for a number of different Io phase angles and Io system III longitudes. The (O I) 6300-A emission brightness exhibits an east-west asymmetry, where the average intensity for Io phase angles in the west (receding ansa) is 1.5 times brighter than in the east (approaching ansa). Similar east-west intensity ratios have also been observed for neutrals near Io and ions in the plasma torus for a number of other optical and ultraviolet emission lines which are excited by electron impact. In addition to the east-west asymmetry, the (O I) 6300-A emission brightness exhibits a strong dependence on the Io system III longitude angle, with a maximum value occurring in the range 200 deg +/- 50 deg. Earlier IUE observations of ultraviolet emission lines of O and S near Io obtained over a number of years have measured the east-west asymmetry, but the long IUE integration times of approximately 7-14 hours masked any detection of system III variability. For the (O I) 6300-A emission, the O(1D) state may be excited by electron impact of atomic oxygen and by electron impact dissociation of SO. The molecule SO may be present at the exobase or may be produced above the exobase as the dominant product of SO2 dissociation by electron impact. Preliminary assessment indicates that production of O(1D) by molecular dissociation may be more important. The (O I) 6300-A emission may therefore provide a remote signature for monitoring (1) the upward transport rates of molecular species in Io's atmosphere, (2) the relative abundance and time-variable dissociation of SO2 and/or SO at the exobase and in the corona of Io, and (3) the spatial distribution of these escaping molecular and atomic species and their ion production rates in the planetary magnetosphere.

Scherb, F.↗

Monte Carlo mixture model of lifetime cancer incidence risk from radiation exposure on shuttle and international space station

Estimating uncertainty in lifetime cancer risk for human exposure to space radiation is a unique challenge. Conventional risk assessment with low-linear-energy-transfer (LET)-based risk from Japanese atomic bomb survivor studies may be inappropriate for relativistic protons and nuclei in space due to track structure effects. This paper develops a Monte Carlo mixture model (MCMM) for transferring additive, National Institutes of Health multiplicative, and multiplicative excess cancer incidence risks based on Japanese atomic bomb survivor data to determine excess incidence risk for various US astronaut exposure profiles. The MCMM serves as an anchor point for future risk projection methods involving biophysical models of DNA damage from space radiation. Lifetime incidence risks of radiation-induced cancer for the MCMM based on low-LET Japanese data for nonleukemia (all cancers except leukemia) were 2.77 (90% confidence limit, 0.75-11.34) for males exposed to 1 Sv at age 45 and 2.20 (90% confidence limit, 0.59-10.12) for males exposed at age 55. For females, mixture model risks for nonleukemia exposed separately to 1 Sv at ages of 45 and 55 were 2.98 (90% confidence limit, 0.90-11.70) and 2.44 (90% confidence limit, 0.70-10.30), respectively. Risks for high-LET 200 MeV protons (LET=0.45 keV/micrometer), 1 MeV alpha-particles (LET=100 keV/micrometer), and 600 MeV iron particles (LET=180 keV/micrometer) were scored on a per particle basis by determining the particle fluence required for an average of one particle per cell nucleus of area 100 micrometer(2). Lifetime risk per proton was 2.68x10(-2)% (90% confidence limit, 0.79x10(-3)%-0. 514x10(-2)%). For alpha-particles, lifetime risk was 14.2% (90% confidence limit, 2.5%-31.2%). Conversely, lifetime risk per iron particle was 23.7% (90% confidence limit, 4.5%-53.0%). Uncertainty in the DDREF for high-LET particles may be less than that for low-LET radiation because typically there is very little dose-rate dependence. Probability density functions for high-LET radiation quality and dose-rate may be preferable to conventional risk assessment approaches. Nuclear reactions and track structure effects in tissue may not be properly estimated by existing data using in vitro models for estimating RBEs. The method used here is being extended to estimate uncertainty in spacecraft shielding effectiveness in various space radiation environments.

NASA Center LaRC↗

Compact Microwave Mercury Ion Clock for Space Applications

We review progress in developing a small Hg ion clock for space operation based on breadboard ion-clock physics package where Hg ions are shuttled between a quadrupole and a 16-pole rf trap. With this architecture we have demonstrated short-term stability approx.1-2x10(exp -13) at 1 second, averaging to 10-15 at 1 day. This development shows that H-maser quality stabilities can be produced in a small clock package, comparable in size to an ultra-stable quartz oscillator required or holding 1-2x10(exp -13) at 1 second. We have completed an ion clock physics package designed to withstand vibration of launch and are currently building a approx. 1 kg engineering model for test. We also discuss frequency steering software algorithms that simultaneously measure ion signal size and lamp light output, useful for long term operation and self-optimization of microwave power and return engineering data.

navigation↗

Magnesium and Titanium Isotopic Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende: It Is Fun

Introduction: Hibonite-rich refractory inclusions are among the first solids that formed in the solar nebula, and thus provide constraints on the earliest environment in the Solar System. An unusual hibonite-perovskite inclusion from Allende, SHAL, consists of a large (approximately 500 by 200 microns) single hibonite crystal and coexisting blocky perovskite (approximately 200 microns in size). The hibonite is characterized by chemical and oxygen isotopic compositions similar to those in the FUN (Fractionated and Unknown Nuclear anomalies) inclusion HAL. However, the rare earth element (REE) patterns measured at different spots of SHAL hibonite are highly variable, ranging from Group II-like (light REEs enriched relative to heavy REEs) to Group III-like (relatively flat with slight Eu depletions), but overall contrast largely with that of HAL, especially in the Ce and Yb abundances. This implies that SHAL hibonite formed and underwent distillation processes under more reducing conditions. Interestingly, the accompanying perovskite has uniform, unfractionated oxygen isotopic compositions (averaging delta (sup 17) O equals delta (sup 18) O equals −7 per mille) and REE abundances that are completely different from those of SHAL hibonite. This has been interpreted that perovskite and hibonite may not be co-genetic. Here we performed Al-Mg and Ti isotopic measurements of SHAL hibonite and perovskite to determine if the FUN characteristics are observed in these two isotope systems, and to further constrain the origin and evolution of SHAL. Results: Isotopic measurements of Al-Mg and Ti in SHAL were performed on the UCLA CAMECA ims-1290 ion microprobe by following the analytical protocols described in [1]. The Al-Mg and Ti data obtained in both terrestrial standards and SHAL hibonite and perovskite are shown below. Both SHAL hibonite and perovskite, despite very high (sup 27) Al to (sup 24) Mg ratios, are devoid of (sup 26) Mg excesses that can be attributed to the decay of (sup 26) Al. Delta (sup 25) Mg (mass-dependent fractionation) in hibonite is approximately −5 per mille per atomic mass unit relative to Madagascar hibonite, but is not well constrained for perovskite due to very large uncertainties owing to extremely low Mg contents. Similar to Mg isotopes, SHAL hibonite and perovskite show essentially the same Ti isotopic compositions, with anomalies in (sup 50) Ti of approximately 14 per mille, but the former shows greater Ti isotope fractionation than the latter (2.5 per mille per atomic mass unit versus 0 per mille). Discussion and Conclusions: The Al-Mg and Ti isotopic compositions of SHAL hibonite are consistent with those of HAL, suggesting that SHAL hibonite is a FUN inclusion and likely formed prior to homogenization of (sup 26) Al and Ti isotope variations in the solar nebula. However, the formation mechanisms for SHAL and HAL differ, given the differences in the REE patterns and degrees of oxygen mass-dependent fractionation. The Group-II to Group-III like REE patterns, the Yb depletions, and negative delta (sup 25) Mg observed in SHAL hibonite are all consistent with condensation of the hibonite precursor in a reducing environment.. The lack of large Ce depletions in SHAL hibonite implies that distillation processes that fractionated hibonite's oxygen isotopes must have taken place under a reducing condition, but the extent to which SHAL hibonite was distilled appears to be less than HAL because of the smaller degree of oxygen mass-dependent fractionation. The perovskite shares essentially the same Ti and Mg isotopic compositions as hibonite and probably formed in the same reservoir.. The ultrarefractory REE pattern seen in perovskite likely resulted from gas-solid fractionation which depleted HREEs in this reservoir. This process also explains why SHAL hibonite is generally depleted in HREEs relative to LREEs.

Liu, M.-C.↗

F2 peak electron density at Millstone Hill and Hobart: Comparsion of theory and measurement at solar maximum

This paper compares the observed behavior of the (F2) layer of the ionosphere at Millstone Hill and Hobart with calculations from the field line interhemispheric plasma (FLIP) model for solar maximum, solstice conditions in 1990. During the study period the daily F(sub 10.7) index varied by more than a factor of 2 (123 to 280), but the 81-day mean F(sub 10.7) (F(sub 10.7 A)) was almost constant near 190. Calculations were performed with and without the effects of vibrationally excited N2 (N(sup *)(sub 2) which affects the loss rate of atomic oxygen ions. In the case without N(sup *)(sub 2) there is generally good agreement between the model and measurement for the daytime, peak density of the F region (NmF2). Both the model and the measurement show a strong seasonal anomaly with the winter noon densities a factor of 3 to 4 greater than the summer noon densities at Millstone Hill and a factor of 2 greater at Hobart. The seasonal anomaly in the model is caused by changes in the neutral composition as given by the mass spectrometer and incoherent scatter (MSIS) 86 neutral density model. There is generally little or no increase in the observed noon NmF2 as a function of daily F(sub 10.7) except at Millstone Hill in winter. In contrast to the generally good agreement between model and data at noon, the model badly underestimates the density at night at Millstone Hill at all seasons. At Hobart the model reproduces the nighttime density variations well in both winter and summer. The international reference ionosphere (IRI) model generally provides a good representation of the average behavior of noon NmF2 and hmF2 but because the data show a lot of day-to-day variability, there are often large differences. The FLIP model is able to reproduce this variability when hmF2 is specified. The IRI model peak densities are better than the FLIP densities at night, but the IRI model does not represent the Millstone Hill summer data very well at night in 1990.

Richards, P. G.↗

Empirical relationships between gas abundances and UV selective extinction

Several studies of gas-phase abundances in lines of sight through the outer edges of dense clouds are summarized. These lines of sight have 0.4 less than E(B-V) less than 1.1 and have inferred spatial densities of a few hundred cm(-3). The primary thrust of these studies has been to compare gaseous abundances in interstellar clouds that have various types of peculiar selective extinction. To date, the most notable result has been an empirical relationship between the CN/Fe I abundance ratio and the depth of the 2200 A extinction bump. It is not clear at the present time, however, whether these two parameters are linearly correlated or the data are organized into two discrete ensembles. Based on 19 samples and assuming the clouds form discrete ensembles, lines of sight that have a CN/Fe I abundance ratio greater than 0.3 (dex) appear to have a shallow 2.57 plus or minus 0.55 bump compared to 3.60 plus or minus 0.36 for other dense clouds and compared to the 3.6 Seaton (1979) average. The difference in the strength of the extinction bump between these two ensembles is 1.03 plus or minus 0.23. Although a high-resolution IUE survey of dense clouds is far from complete, the few lines of sight with shallow extinction bumps all show preferential depletion of certain elements, while those lines of sight with normal 2200 A bumps do not. Ca II, Cr II, and Mn II appear to exhibit the strongest preferential depletion compared to S II, P II, and Mg II. Fe II and Si II depletions also appear to be enhanced somewhat in the shallow-bump lines of sight. It should be noted that Copernicus data suggest all elements, including the so-called nondepletors, deplete in diffuse clouds (Snow and Jenkins 1980, Joseph 1988). Those lines of sight through dense clouds that have normal 2200 A extinction bumps appear to be extensions of the depletions found in the diffuse interstellar medium. That is, the overall level of depletion is enhanced, but the element-to-element abundances are similar to those in diffuse clouds. In a separate study, the abundances of neutral atoms were studied in a dense cloud having a shallow 2200 A bump and in one with a normal strength bump.

Joseph, Charles L.↗

Gamma-ray observations of Ophiuchus with EGRET: The diffuse emission and point sources

Observations of the Ophiuchus region made with the Energetic Gamma-Ray Experiment Telescope (EGRET) on the Compton Gamma Ray Observatory (CGRO) during the first 2 1/2 years of operation show the diffuse emission from the interstellar gas in Ophiuchus as well as variable emission from two point sources. The gamma-ray emission is modeled in terms of cosmic-ray interactions with atomic and molecular hydrogen in Ophiuchus and with low-energy photons along the line of sight. The model also includes the flux from the two point sources and an isotropic diffuse contribution. The cosmic-ray density is assumed to be uniform. The derived ratio of molecular hydrogen column density to integrated CO intensity is (1.1 +/- 0.2) x 10(exp 20) H-mols/sq cm (K km/s)(exp -1). At the sensitivity and resolution of the gamma-ray data, no variation of this ratio over the modeled region is discernible, nor are any regions of enhanced cosmic-ray density apparent. The model was fitted to seven narrow energy bands to obtain the energy depedence of the gamma-ray production function and the spectra of the point sources. The derived production function is in good agreement with theoretical calculations and the local cosmic-ray electron and proton spectra. The positions of the point sources were determined from maximum likelihood analysis of the gamma-ray emission observed in excess of the diffuse model. We identify one point source with the quasar PKS 1622-253, which has an average flux, E greater than 100 MeV, of (2.5 +/- 0.5) x 10(exp -7) photons/sq cm/s and photon spectral index -1.9 +/- 0.3. The other source, denoted GRO J1631-27, has not yet been identified at other wavelengths. Its average flux, E greater than 100 MeV, is (1.1 +/- 0.4) x 10(exp -7) photons/sq cm/s; however, its spectral index is poorly determined. The spectral index and intensity of the isotropic contribution to the model agree well with the extragalactic diffuse emission derived from the SAS 2 data.

Hunter, S. D.↗

Photochemistry of Saturn's Atmosphere: Hydrocarbon Chemistry and Comparisons with ISO Observations - 1

To investigate the details of hydrocarbon photochemistry on Saturn, we have developed a one-dimensional diurnally averaged model that couples hydrocarbon and oxygen photochemistry, molecular and eddy diffusion, radiative transfer, and condensation. The model results are compared with observations from the Infrared Space Observatory (ISO) to place tighter constraints on molecular abundances, to better define Saturn's eddy diffusion coefficient profile, and to identify important chemical schemes that control the abundances of the observable hydrocarbons in Saturn's upper atmosphere. From the ISO observations, we determine that the column 12 densities of CH3, CH3C2H, and C4H2 above 10 mbar are 4 (sup +2) (sub -1.5) x 10 (exp 13) cm (sup -2), (1.1 plus or minus 0.3) x 10 (exp 15) cm (exp -2), and (1.2 plus or minus 0.3) x 10 (exp 14) cm (sup -2), respectively. The observed ISO emission features also indicate C2H2 mixing ratios of 1.2 (sup +0.9) (sub -0.6) x 10 (exp -6) at 0.3 mbar and (2.7 plus or minus 0.8) x 10 (exp -7) at 1.4 mbar, and a C2H6 mixing ratio of (9 plus or minus 2.5) x 10 (exp -6) at 0.5 mbar. Upper limits are provided for C2H4, CH2CCH2, C3H8, and C6H2 sensitivity of the model results to variations in the eddy diffusion coefficient profile, the solar flux, the CH4 photolysis branching ratios, the atomic hydrogen influx, and key reaction rates are discussed in detail. We find that C4H2 and CH3C2H are particularly good tracers of important chemical processes and physical conditions in Saturn's upper atmosphere, and C2H6 is a good tracer of the eddy diffusion coefficient in Saturn's lower stratosphere. The eddy diffusion coefficient must be smaller than approximately 3 x 10 (exp 4) sq cm s (sup -1) at pressures greater than 1 mbar in order to reproduce the C2H6 abundance inferred from ISO observations. The eddy diffusion coefficients in the upper stratosphere could be constrained by observations of CH3 radicals if the low-temperature chemistry of CH3 were better understood. We also discuss the implications of our modeling for aerosol formation in Saturn's lower stratosphere-diacetylene, butane, and water condense between approximately 1 and 300 mbar in our model and will dominate stratospheric haze formation at nonauroral latitudes. Our photochemical models will be useful for planning observational sequences and for analyzing data from the upcoming Cassini mission.

Moses, Julianne I.↗

An NMR study of microvoids in polymers

An understanding of polymer defect structures, like microvoids in polymeric matrices, is crucial to their fabrication and application potential. In this project guest atoms are introduced into the microvoids in PMR-15 and NMR is used to determine microvoid sizes and locations. Xenon is a relatively inert probe that would normally be found naturally in polymer or in NMR probe materials. There are two NMR active xenon isotopes, Xe-129 and Xe-131. The Xe atom has a very high polarizability, which makes it sensitive to the intracrystalline environment of polymers. Interactions between the Xe atoms and the host matrix perturb the Xe electron cloud, deshielding the nuclei, and thereby expanding the range of the observed NMR chemical shifts. This chemical shift range which may be as large as 5000 ppm, permits subtle structural and chemical effects to be studied with high sensitivity. The Xe(129)-NMR line shape has been found to vary in response to changes in the pore symmetry of the framework hosts line Zeolites and Clathrasil compounds. Before exposure to Xe gas, the PMR-15 samples were dried in a vacuum oven at 150 C for 48 hours. The samples were then exposed to Xe gas at 30 psi for 72 hours and sealed in glass tubes with 1 atmosphere of xenon gas. Xenon gas at 1 atmosphere was used to tune up the spectrometer and to set up the appropriate NMR parameters. A single Xe-129 line at 83.003498 Mhz (with protons at 300 Mhz) was observed for the gas. With the xenon charged PMR-15 samples, a second broader line is observed 190 ppm downfield from the gas line (also observed). The width of the NMR line from the Xe-129 absorbed in the polymer is at least partially due to the distribution of microvoid sizes. From the chemical shift (relative to the gas line) and the line width, we estimate the average void sizes to be 2.74 +/- 0.20 angstroms. Since Xe-129 has such a large chemical shift range (approximately 5000 ppm), we expect the chemical shift anisotropy to contribute to the line width (delta upsilon = 2.5 kHz).

Toy, James↗

Miniaturized Mercury Ion Clock for Ultrastable Deep Space Applications

We have recently completed a prototype ion-clock physics package based on Hg ions shuttled between a quadrupole and a 16-pole rf trap. With this architecture we have demonstrated short-term stability ~2-3x10-13 at 1 second, averaging to 10-15 at 1 day. This development shows that H-maser quality stabilities can be produced in a small clock package, comparable in size to an ultra-stable quartz oscillator required for holding 1-2x10-13 at 1 second. This performance was obtained in a sealed vacuum configuration where only a getter pump was used to maintain vacuum. The vacuum tube containing the traps has now been under sealed vacuum conditions for nearly 1.5 years with no measurable degradation of ion trapping lifetimes or clock short-term performance. Because the tube is sealed, the Hg source and Neon buffer gas are held indefinitely, for the life of the tube. There is no consumption of Hg in this system unlike in a Cs beam tube where lifetime is often limited by Cs depletion.

mercury ion clocks↗

Characterization of Magnetoacoustic Emission Related to Structural Properties of Ferromagnets

An extensive study of magnetoacoustic emission (MAE) properties has been performed over the past several years. As a result, the dependence of the spectral characteristics of MAE on certain microstructural variations and uniaxially applied stress in a particular type of low carbon steel are now well known. The embrittlement-causing concentration of certain atomic species, e. g., tin, sulphur, phosphorous etc., at the grain boundaries of this steel creates strong potential barriers resisting the motion of non-180 domain walls which is the source of MAE. (Since the only type of non-180 domain walls in this material are 90 domain walls, the term 90 domain wall will be used throughout this paper in place of non-180 domain wall.) An MAE burst produced during one-half cycle of a hysteresis loop at a low AC magnetic field frequency (e. g., 0.7 Hz) shows two sub-peaks; the leading peak is usually sharp and short-lived, while the trailing peak is usually smooth and long-lasting. It has been shown that the enhanced domain wall-defect interaction, due to the strengthened potential barriers, causes an increase in the asymmetry of the MAE signal by suppressing the leading sub-peak and amplifying the trailing sub-peak. This phenomena is due to the delayed motion of the 90 domain walls. The effect of a tensile stress applied parallel to the external AC magnetic field is to diminish the MAE. On the other hand, the amplitude of the MAE burst has been shown to be a non-monotonic function of the stress amplitude. Recently, our study has concentrated on obtaining quantitative values for parameters computed from the MAE spectra averaged over a sufficient number of cycles to achieve statistical stability. Nevertheless, certain fundamental elements of the MAE characteristics remain unexplained.

Namkung, M.↗

Interstellar PAH emission in the 11-14 micron region: new insights from laboratory data and a tracer of ionized PAHs

The Ames infrared spectral database of isolated, neutral and ionized polycyclic aromatic hydrocarbons (PAHS) shows that aromatic CH out-of-plane bending frequencies are significantly shifted upon ionization. For solo- and duet-CH groups, the shift is pronounced and consistently toward higher frequencies. The solo-CH modes are blueshifted by an average of 27 cm-1 and the duet-CH modes by an average of 17 cm-1. For trio- and quartet-CH groups, the ionization shifts of the out-of-plane modes are more erratic and typically more modest. As a result of these ionization shifts, the solo-CH out-of-plane modes move out of the region classically associated with these vibrations in neutral PAHS, falling instead at frequencies well above those normally attributed to out-of-plane bending, vibrations of any type. In addition, for the compact PAHs studied, the duet-CH out-of-plane modes are shifted into the frequency range traditionally associated with the solo-CH modes. These results refine our understanding of the origin of the dominant interstellar infrared emission feature near 11.2 microns, whose envelope has traditionally been attributed only to the out-of-plane bending of solo-CH groups on PAHS, and provide a natural explanation for the puzzling emission feature near 11.0 microns within the framework of the PAH model. Specifically, the prevalent but variable long-wavelength wing or shoulder that is often observed near 11.4 microns likely reflects the contributions of duet-CH units in PAH cations. Also, these results indicate that the emission between 926 and 904 cm-1 (10.8 and 11.1 microns) observed in many sources can be unambiguously attributed to the out-of-plane wagging, of solo-CH units in moderately sized (fewer than 50 carbon atom) PAH cations, making this emission an unequivocal tracer of ionized interstellar PAHS.

Astronomy↗

Interstellar PAH Emission in the 11-14 micron Region: New Insights and a Tracer of Ionized PAHs

The Ames infrared spectral database of isolated, neutral and ionized polycyclic aromatic hydrocarbons (PAHs) shows that aromatic CH out-of-plane bending frequencies are significantly shifted upon ionization. For non-adjacent and doubly-adjacent CH groups, the shift is pronounced and consistently toward higher frequencies. The non-adjacent modes are blueshifted by an average of 27 per cm and the doubly-adjacent modes by an average of 17 per cm. For triply- and quadruply-adjacent CH out-of-plane modes the ionization shifts are more erratic and typically more modest. As a result of these ionization shifts, both the non-adjacent and doubly-adjacent CH out-of-plane modes move out of the regions classically associated with their respective vibrations in neutral PAHs. The doubly-adjacent modes of ionized PAHs tend to fall into the frequency range traditionally associated with the non-adjacent modes, while the non-adjacent modes are shifted to frequencies above those normally attributed to out-of-plane bending vibrations. Consequently, the origin of the interstellar infrared emission feature near 11.2 microns, traditionally attributed to the out-of-plane bending of non-adjacent CH groups on PAHs is rendered ambiguous. Instead, this feature likely reflects contributions from both non-adjacent CH units in neutral PAHs and doubly-adjacent CH units in PAH cations, the dominant charge state in the most energetic emission regions. This greatly relieves the structural constraints placed on the interstellar PAH population by the dominance of the 11.2 micron band in this region and eliminates the necessity to invoke extensive dehydrogenation of the emitting species. Furthermore, these results indicate that the emission between 926 and 904 per cm (10.8 and 11.1 microns) observed in many sources can be unambiguously attributed to the non-adjacent CH out-of-plane bending modes of moderately-sized (fewer than 50 carbon atom) PAH cations making this emission an unequivocal tracer of ionized interstellar PAHs.

Hudgins, Douglas M.↗

Compact Microwave Mercury Ion Clock for Space Applications

We have recently completed a breadboard ion-clock physics package based on Hg ions shuttled between a quadrupole and a 16-pole rf trap. With this architecture we have demonstrated short-term stability approximately 1 - 2 x 10(exp -13) at 1 second, averaging to 10(exp -15) at 1 day. This development shows that H-maser quality stabilities can be produced in a small clock package, comparable in size to an ultra-stable quartz oscillator required for holding 1 - 2 x 10(exp -13) at 1 second. This performance was obtained in a sealed vacuum configuration where only a getter pump was used to maintain vacuum. The vacuum tube containing the traps has now been under sealed vacuum conditions for nearly three years with no measurable degradation of ion trapping lifetimes or clock short-term performance. We have fabricated the vacuum tube, ion trap and UV windows from materials that will allow an approximately 400 C bake-out to prepare for tube seal-off. This approach to the vacuum follows the methods used in flight vacuum tube electronics, such as flight TWTA's where tube operation lifetime and shelf life of up to 15 years is achieved.

Atomic Clock↗