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At least 127 records · Page 7

The infrared spectra of nitriles and related compounds frozen in Ar and H2O

We present the 2320-2050 cm-1 (4.31-4.88 micrometers) infrared spectra of 16 solid-state nitriles, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C triple bond N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile (phenylcyanide), 9-anthracenecarbonitrile, dimethylcyanamide, isopropylnitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyruvonitrile, dicyandiamide, cyanamide, n-butylisocyanide, methylisocyanoacetate, diisopropylcarbodiimide, and hydrogen cyanide. The C triple bond N stretching bands of the majority of nitriles fall in the 2300-2200 cm-1 (4.35-4.55 micrometers) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contrast, the isonitriles and a few exceptional nitriles and related species produce bands at lower frequencies spanning the 2200-2080 cm-1 (4.55-4.81 micrometers) range. These features also have similar positions in both Ar and H2O matrices, and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C triple bond N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165 cm-1 (4.62 micrometers) "XCN" interstellar feature and the 4550 cm-1 (2.2 micrometers) feature of various objects in the solar system are discussed.

NASA Center ARC↗

Ar-40/Ar-39 Ages of Maskelynite Grains from ALHA 77005

We present Ar-40/Ar-39 measurements for twelve small (20-60 micro-g) maskelynite samples from the heavily shocked martian meteorite ALHA 77005. The reported modal composition for ALHA 77005 is 50-60% olivine (Fa28), 30-40% pyroxene (Wo5Fs23En72), approx.8% maskelynite (An53), and approx.2% opaques by volume [1]). The meteorite is usually classified as a lherzolite. Previous Studies - Ar-40/Ar-39 results from previous work display disturbed release spectra [2,3]. In study [2], Ar-40/Ar-39 measurements on a 52-mg whole-rock sample produced an extremely disturbed release spec-trum, with all calculated apparent ages > 1 Ga, (Fig. 1). In a subsequent study [3], a light and a dark phase were analyzed. A 2.3-mg sample of the light, relatively low-K phase produced a disturbed release spectrum. For the first 20% of the Ar-39(sub K), most of the apparent ages exceeded >1 Ga; the remaining 80% yielded ages between 0.3-0.5 Ga. The integrated age for this phase is 0.9 Ga.

Turrin, B.↗

Calculation of ion–ion mutual neutralization rate constants using Landau–Zener theory coupled with trajectory simulations for Ar + –Cl − , Br − , I −

In this computational study, we self-consistently calculate the rate constants of mutual neutralization reactions by incorporating the electron transfer probability, using Landau–Zener state transition theory with inputs derived from ab initio quantum chemistry calculations, into classical trajectory simulations. Electronic structure calculations are done using correlation consistent basis sets with multi-reference configuration interaction to map all the molecular electronic states below the ion-dissociation limit as a function of the distance between the reacting species. Our electronic structure calculations have been significantly improved from our previous work through improved selection of molecular electronic configurations maintaining a fine grid of 1a 0 over a wide range of bond lengths and accurate treatment of spin–orbit couplings. Non-adiabatic coupling matrix elements are calculated with the three-point central difference method near each avoided crossing to estimate the exact crossing point R x and coupling parameter H if , which are inputs to the multi-channel Landau–Zener theory to calculate the electron transition probability. Our approach is applied to estimate the mutual neutralization rate constants for the following ion pairs: Ar + –Cl − , Ar + –Br − , Ar + –I − at ∼133 Pa. Furthermore, our predictions are compared against the experimental data reported. It is seen that the improvement in the electronic structure calculation results in excellent agreement between the simulation results and the available experimental data to within a factor of ∼2 or ∼±50%.

Complete-active space self-consistent field↗

Spatial distribution of Ar-40/Ar-39 ages in lunar breccia 14301.

The distribution of stable and radioactive argon isotopes in a lunar breccia has been measured in situ by laser probe mass spectrometry. This new technique determines the spatial distribution of Ar-40/Ar-39 ages on less than .1 milligram of material. Calculated Ar-40/Ar-39 ages of clasts within this breccia are 3.7 and 2.9 b.y. Parentless radiogenic Ar-40 exists within the fine-grained matrix and appears to have been trapped simultaneously with solar argon. This 'atmosphere' of ambient gas appears to have been incorporated into the rock by an impact event not more than 3 b.y. ago.

Megrue, G. H.↗

Studies of K-Ar dating and xenon from extinct radioactivities in breccia 14318; implications for early lunar history

The lunar breccia 14318 is one of three Apollo-14 breccias containing substantial amounts of parentless xenon from the spontaneous fission of extinct Pu-244. The argon and xenon contained in this breccia were studied by stepwise heating of pristine and neutron-irradiated samples. The isotopic composition of xenon from fission, determined by an improved method, is shown to be from Pu-244. Concentrations of this fissiogenic xenon are in substantial excess (15-fold) of what could be produced by spontaneous fission of U-238. The breccia is found to contain abundant trapped argon with an Ar-40/Ar-36 ratio of roughly 14. Otherwise, the argon is radiogenic and gives a convincing K-Ar age of 3.69 plus or minus 0.09 b.y. by the stepwise Ar-40/Ar-39 method, nearly in agreement with ages for other Apollo-14 breccias.

Reynolds, J. H.↗

Ar-40/Ar-39 chronology and cosmic ray exposure ages of the Apollo 15 samples

The Ar-40*/Ar-39* thermal release patterns of igneous soil fragments, rake basalts, and large crystalline rocks are by and large well defined. Shock deformations of up to moderate intensities have no observable effects on the Ar-40*/Ar-39* release patterns. Neither do the Ar-40* diffusion losses have any relationship with the shock intensities. The peak of the magnetic activity in Palus Putredinis occurred at 3.33 plus or minus 0.02 Gy, lava flows continuing up to 3.13 Gy but at much reduced intensity. No correlation between the crystallization ages and the petrographic rock types was observed. The cosmic ray exposure gas indicate a mature regolith around the Hadley Rille-Apennine Front region. The exposure ages of the Apollo 15 samples cannot reliably be used to obtain the time of prominent cratering events at this site.

Husain, L.↗

Titanium spallation cross sections between 30 and 584 MeV and Ar-39 activities on the moon

The production cross sections of Ar-39 for Ti spallation at 45-, 319-, 433-, and 584-MeV proton energies were measured to be 0.37 + or - 09, 12.4 + or - 3.7, 9.1 + or - 2.7, and 17.8 + or - 6.2 mb, respectively. Normalized Ar-39 production rates and activities are also derived for protons above 40 Mev and for three differential proton spectra. It is concluded that even for samples of high-Ti content, Ti spallation by solar protons below 200-MeV energy does not contribute significantly to their Ar-39 radioactivity.

Steinbrunn, F.↗

Ar-40 intercept values and young apparent /K-40/-/Ar-40/ ages of five Apollo 15 fines

Correlations between Ar-40 and Ar-36 from size fractions of three Apollo 15 fines (15071, 15421, 15501) have been obtained. The Ar-40 intercept values of these fines and of 15091 and 15601 are generally lower than what one would expect for fines resulting from the comminution of rocks having ages of about 3.3 billion yr, typical for basalts of the landing site. This is interpreted to be the result of contamination by ray material from the Copernican age (equal or less than about 1 billion yr) craters, Autolycus and Aristillus, north of the landing site.

Jordan, J. L.↗

Rate constants for the deactivation of O/1D/ by Xe, Kr, and Ar over the range 110-330 K

The rate constants for the deactivation of O(1D) by Xe, Kr, and Ar were measured over the range 110-330 K. Only Xe had a significant temperature dependence. Its Arrhenius expression is (8.5 + or - 1.7) times 10 to the -11th power exp(-103 + or - 52)/RT cu cm/molecule-sec. The rate constants for Kr and Ar are (6.4 + or - 1.3) times 10 to the -12th power and (5.0 + or - 1.5) times 10 to the -13th power cu cm/molecule-sec, respectively. The observed trend in deactivation efficiency, Xe (greatest), Kr, Ar (least), and the observed temperature effects support the results and the spin-orbit interaction mechanism for deactivation given by Husain and co-workers.

Davidson, J. A.↗

Auger electron emission due to incident particle in Ar(+), Ne(+) and Na(+) collisions with different solid targets

The L23 Auger spectra of Ar, Ne and Na from Ar(+)-Ti, Ne(+)-Mg, Ne-A1, Na(+)-Be, Na(+)-Mg and Na(+)-A1 collisions were obtained. For Ar, L23 MM Auger electrons are emitted from the fast moving incident projectiles and a Doppler broadened structure is observed. The Ne and Na Auger spectra are due to Auger transitions with single or double 2p vancancies in the initial state of the implanted Ne atoms or surface trapped Na atoms.

Benazeth, C.↗

Ar-40/Ar-39 and U-Th-Pb dating of separated clasts from the Abee E4 chondrite

Ar-40/Ar-39 and U-Th-Pb are investigated for three clasts from the Abee (E4) enstatite chondrite, yielding Ar-40/Ar-39 plateau ages (and/or maximum ages) of 4.5 Gy, while two of the clasts give average ages of 4.4 Gy. The 4.4-4.5 Gy range does not resolve possible age differences among the clasts. The U-Th-Pb data are consistent with the interpretation that initial clast formation occurred 4.58 Gy ago, and that the clasts have since remained closed systems which have been contaminated with terrestrial Pb. The thermal history of Abee deduced from Ar data seems consistent with that deduced from magnetic data, suggesting that various Abee components experienced separate histories until brecciation no later than 4.4 Gy ago, experiencing no significant subsequent heating.

Bogard, D. D.↗

Solubility and partitioning of Ar in anorthite, diopside, forsterite, spinel, and synthetic basaltic liquids

The solubility and partitioning of Ar in natural anorthite, diopside, forsterite, spinel, and synthetic iron-free basaltic melts was investigated using a new technique that obviates the postquenching phase separation. It was found that the solubility of Ar in the minerals was surprisingly high. Moreover, the solubility of Ar in different samples of a particular mineral run in the same experiment varied more than the solubility in the same sample run in different experiments, suggesting that noble gases are held in lattice vacancy defects. Moreover, the results of TEM imaging revealed no anomalous microstructures, while EXAFS studies of some samples showed that Kr has no preferred site in the lattices, supporting the defect siting conclusion.

Broadhurst, C. Leigh↗

Coeval Ar-40/Ar-39 ages of 65.0 million years ago from Chicxulub crater melt rock and Cretaceous-Tertiary boundary tektites

Ar-40/Ar-39 dating of drill-core samples of a glassy melt rock recovered from beneath a massive impact breccia contained with the 180-kilometer subsurface Chicxulub crater yields well-behaved incremental heating spectra with a mean plateau age of 64.98 +/- 0.05 million years ago (Ma). The glassy melt rock of andesitic composition was obtained from core 9 (1390 to 1393 meters) in the Chicxulub 1 well. The age of the melt rock is virtually indistinguishable from Ar-40/Ar-39 ages obtained on tektite glass from Beloc, Haiti, and Arroyo el Mimbral, northeastern Mexico, of 65.01 +/- 0.08 Ma (mean plateau age for Beloc) and 65.07 +/- 0.10 Ma (mean total fusion age for both sites). The Ar-40/Ar-39 ages, in conjunction with geochemical and petrological similarities, strengthen the suggestion that the Chicxulub structure is the source for the Haitian and Mexican tektites and is a viable candidate for the Cretaceous-Tertiary boundary impact site.

Swisher, Carl C., III↗

Ar-40/Ar-39 age spectra of Apollo 15 impact melt rocks by laser step-heating and their bearing on the history of lunar basin formation

Results are reported on 26 high-resolution (16-51 steps) Ar-40/Ar-39 age spectra obtained on 12 Apollo-15 melt rocks of different composition using a continuous laser system on submg fragments of recrystallized melt and single-crystal plagioclase clasts from impact melt rocks collected at the Apennine Front where the Imbrium and Serenitatis basins intersect. A table is presented with the summary of the Ar-40/Ar-39 spectrum data, which represent 891 individual temperature step analyses. Also presented are 20 of the 26 age spectra along with their respective K/Ca plots. Melt rock fragments and plagioclase clasts from seven of the 12 samples analyzed yielded reproducible, intermediate-T Ar-40/Ar-39 age spectrum plateaus, which were interpreted as crystallization ages that represent the times of impact of bolides onto the lunar surface.

Dalrymple, G. B.↗

A generic interface element for COMET-AR

The implementation of an interface element capability within the COMET-AR software system is described. The report is intended for use by both users of currently implemented interface elements and developers of new interface element formulations. Guidance on the use of COMET-AR is given. A glossary is provided as an Appendix to this report for readers unfamiliar with the jargon of COMET-AR. A summary of the currently implemented interface element formulation is presented in Section 7.3 of this report.

Mccleary, Susan L.↗

Mass Spectrometric and Langmuir Probe Measurements in Inductively Coupled Plasmas in Ar, CHF3/Ar and CHF3/Ar/O2 Mixtures

Absolute fluxes and energy distributions of ions in inductively coupled plasmas of Ar, CHF3/Ar, and CHF3/Ar/O2 have been measured. These plasmas were generated in a Gaseous Electronics Conference (GEC) cell modified for inductive coupling at pressures 10-50 mTorr and 100-300 W of 13.56 MHz radio frequency (RF) power in various feedgas mixtures. In pure Ar plasmas, the Ar(+) flux increases linearly with pressure as well as RF-power. Total ion flux in CHF3 mixtures decreases with increase in pressure and also CHF3 concentration. Relative ion fluxes observed in the present studies are analyzed with the help of available cross sections for electron impact ionization and charge-exchange ion-molecule reactions. Measurements of plasma potential, electron and ion number densities, electron energy distribution function, and mean electron energy have also been made in the center of the plasma with a RF compensated Langmuir probe. Plasma potential values are compared with the mean ion energies determined from the measured ion energy distributions and are consistent. Electron temperature, plasma potential, and mean ion energy vary inversely with pressure, but increase with CHF3 content in the mixture.

Kim, J. S.↗

The Infrared Spectra of Nitriles and Related Compounds Frozen in Ar and H2O

We present the 2320-2050/cm (4.31-4.88 micron) infrared spectra of 16 solid state nitrites, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C(is congruent to)N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile phenylcyanide) 9-anthracenecarbonitrile, dimethylcyanamide, isopropy1nitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyr-uvonitrile, dicyandiamide, cyanamide, n-butyfisocyanide, methylisocyanoacetate, dilsopropylcarbodiimide, and hydrogen cyanide. The C(is congruent to)N stretching bands of the majority of nitrites fall in the 2300-2200/cm (4.35-4.55 micron) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contest, the isonitriles and a few exceptional nitrites and related species produce bands at lower frequencies spanning the 2200-2080/cm (4.55-4.81 micron) range. These features also have similar positions in both Am and H2O matrices and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C(is congruent to)N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165/cm (4.62 micron) "XCN" interstellar feature and the 4550/cm (2.2 micron) feature of various objects in the solar system are discussed.

Bernstain, Max P.↗

Ar-40/Ar-39 Age of Hornblende-bearing R Chondrite LAP 04840

Chondrites have a complex chronology due to several variables affecting and operating on chondritic parent bodies such as radiogenic heating, pressure and temperature variation with depth, aqueous alteration, and shock or impact heating [1]. Unbrecciated chondrites can record ages from 4.56 to 4.4 Ga that represent cooling in small parent bodies. Some brecciated chondrites exhibit younger ages (<<4 to 4.4 Ga) that may reflect the age of brecciation, disturbance, or shock and impact events (<< 4 Ga). A unique R chondrite was recently found in the LaPaz Icefield of Antarctica - LAP 04840 [2]. This chondrite contains approx.15% hornblende and trace amounts of biotite, making it the first of its kind. Studies have revealed an equigranular texture, mineral equilibria yielding equilibration near 650-700 C and 250-500 bars, hornblende that is dominantly OH-bearing (very little Cl or F), and high D/H ratios [8,9,10]. To help gain a better understanding of the origin of this unique sample, we have measured the Ar-40/Ar-39 age. Age of 4.290 +/- 0.030 Ga is younger than one would expect for a sample that has cooled within a small body [4], and one might instead attribute the age to a younger shock event, On the other hand, there is no evidence for extensive shock in this meteorite (shock stage S2; [3]), so this sample may have been reannealed after the shock event. This age is similar to Ar-Ar ages determined for some other R chondrites

Righter, K.↗