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At least 181 records · Page 10

Delayed detonation models for normal and subluminous type Ia sueprnovae: Absolute brightness, light curves, and molecule formation

We compute optical and infrared light curves of the pulsating class of delayed detonation models for Type Ia supernovae (SN Ia's) using an elaborate treatment of the Local Thermodynamic Equilbrium (LTE) radiation transport, equation of state and ionization balance, expansion opacity including the cooling by CO, Co(+), and SiO, and a Monte Carlo gamma-ray deposition scheme. The models have an amount of Ni-56 in the range from approximately or equal to 0.1 solar mass up to 0.7 solar mass depending on the density at which the transition from a deflagration to a detonation occurs. Models with a large nickel production give light curves comparable to those of typical Type Ia supernovae. Subluminous supernovae can be explained by models with a low nickel production. Multiband light curves are presented in comparison with the normally bright event SN 1992bc and the subluminous events Sn 1991bg and SN 1992bo to establish the principle that the delayed detonation paradigm in Chandrasekhar mass models may give a common explosion mechanism accounting for both normal and subluminous SN Ia's. Secondary IR-maxima are formed in the models of normal SN Ia's as a photospheric effect if the photospheric radius continues to increase well after maximum light. Secondary maxima appear later and stronger in models with moderate expansion velocities and with radioactive material closer to the surface. Model light curves for subluminous SN Ia's tend to show only one 'late' IR-maximum. In some delayed detonation models shell-like envelopes form, which consist of unburned carbon and oxygen. The formation of molecules in these envelopes is addressed. If the model retains a C/O-envelope and is subluminous, strong vibration bands of CO may appear, typically several weeks past maximum light. CO should be very weak or absent in normal Sn Ia's.

Hoflich, P.↗

Fourier Transform Ultraviolet Spectroscopy of the A Pi-2(3/2) Direct Current X Pi-2(3/2) Transition of BrO

The first spectra of the A (2)Pi(sub 3/2) from X (2)Pi(sub 3/2) electronic transition of BrO using Fourier transform ultraviolet spectroscopy are obtained. Broadband vibrational spectra acquired at 298 +/- 2 K and 228 +/- 5 K, as well as high-resolution rotational spectra of the A from X 7,0 and 12,0 vibrational bands are presented. Wavenumber positions for the spectra are obtained with high accuracy, and cross section assignments are made, incorporating the existing literature. With 35 cm(exp -1) (0.40 nm) resolution the absolute cross section at the peak of the 7,0 band is determined to be (1.58 +/- 0.12) x 10(exp -17) sq cm/molecule at 298 +/- 2 K and (1.97 +/- 0.15) x 10(exp -17) sq cm/molecule at 228 +/- 5 K. BrO dissociation energies are determined with a graphical Birge-Sponer technique, using Le Roy-Bernstein theory to place an upper limit on the extrapolation. From the ground-state dissociation energy, D(sub o)" = 231.0 +/- 1.7 kJ/mol, the heat of formation of BrO(g) is calculated, del(sub f)H(0 K) = 133.7 +/- 1.7 kJ/mol and del(sub f)H(298.15 K) = 126.2 +/- 1.7 kJ/mol. Cross sections for the high-resolution 7,0 and 12,0 rotational peaks are the first to be reported. The band structures are modeled, and improved band origins, rotational constants, centrifugal distortion constants, and linewidths are determined. In particular, J-dependent linewidths and lifetimes are observed for the both the 7,0 and 12,0 bands.

Wilmouth, David M.↗

Theoretical Chemistry At NASA Ames Research Center

The theoretical work being carried out in the Computational Chemistry Branch at NASA Ames will be overviewed. This overview will be followed by a more in-depth discussion of our theoretical work to determine molecular opacities for the TiO and water molecules and a discussion of our density function theory (DFT) calculations to determine the harmonic frequencies and intensities to the vibrational bands of polycyclic aromatic hydrocarbons (PAHs) to assess their role as carriers to the unidentified infrared (UIR) bands. Finally, a more in-depth discussion of our work in the area of computational molecular nanotechnology will be presented.

Langhoff, Stephen↗

An Accurate Potential Energy Surface for H2O

We have carried out extensive high quality ab initio electronic structure calculations of the ground state potential energy surface (PES) and dipole moment function (DMF) for H2O. A small adjustment is made to the PES to improve the agreement of line positions from theory and experiment. The theoretical line positions are obtained from variational ro-vibrational calculations using the exact kinetic energy operator. For the lines being fitted, the root-mean-square error was reduced from 6.9 to 0.08 /cm. We were then able to match 30,092 of the 30,117 lines from the HITRAN 96 data base to theoretical lines, and 80% of the line positions differed less than 0.1 /cm. About 3% of the line positions in the experimental data base appear to be incorrect. Theory predicts the existence of many additional weak lines with intensities above the cutoff used in the data base. To obtain results of similar accuracy for HDO, a mass dependent correction to the PH is introduced and is parameterized by simultaneously fitting line positions for HDO and D2O. The mass dependent PH has good predictive value for T2O and HTO. Nonadiabatic effects are not explicitly included. Line strengths for vibrational bands summed over rotational levels usually agree well between theory and experiment, but individual line strengths can differ greatly. A high temperature line list containing about 380 million lines has been generated using the present PES and DMF

Schwenke, David W.↗

Ab Initio Calculations of Water Line Strengths

We report on the determination of a high quality ab initiu potential energy surface (PES) and dipole moment function for water. This PES is empirically adjusted to improve the agreement between the computed line positions and those from the HITRAN 92 data base with J less than 6 for H2O. The changes in the PES are small, nonetheless including an estimate of core (oxygen 1s) electron correlation greatly improves the agreement with experiment. Using this adjusted PES, we can match 30,092 of the 30,117 transitions in the HITRAN 96 data base for H2O with theoretical lines. The 10,25,50,75, and 90 percentiles of the difference between the calculated and tabulated line positions are -0.11, -0.04, -0.01, 0.02, and 0.07 l/cm. Non-adiabatic effects are not explicitly included. About 3% of the tabulated line positions appear to be incorrect. Similar agreement using this adjusted PES is obtained for the oxygen 17 and oxygen 18 isotopes. For HDO, the agreement is not as good, with root-mean-square error of 0.25 l/cm for lines with J less than 6. This error is reduced to 0.02 l/cm by including a small asymmetric correction to the PES, which is parameterized by simultaneously fitting to HDO md D2O data. Scaling this correction by mass factors yields good results for T2O and HTO. The intensities summed over vibrational bands are usually in good agreement between the calculations and the tabulated results, but individual lines strengths can differ greatly. A high temperature list consisting of 307,721,352 lines is generated for H2O using our PES and dipole moment function.

Schwenke, David W.↗

Measurements of Line Positions and Strengths of HD O-18 and D2 O-18 in the 2500-4280 cm(exp -1) Region

Measurements of line positions and strengths of D2 O-18 and HD O-18 were obtained with a Fourier transform spectrometer. The data were analyzed to obtain energy levels of the (100), (020), and (001) vibrational states of HD O-18 and the (001) and (011) states of D2 O-18 and the vibrational bands of these states connected to the ground state covered the spectral region from 2500 to 4278 cm(exp -1). 456 absorption lines of D2 O-18 and 856 lines of HD O-18 were assigned from the spectra. The measurements were of oxygen-18 enriched samples of deuterated water vapor and the spectra also contained features of HD O-16, D2 O-16, H2 O-16, H2 O-17 and H2 O-18 of which several were used as frequency calibration standards.

Fourier transform spectrometer (FTS)↗

Highly Accurate Potential Energy Surface, Dipole Moment Surface, Rovibrational Energy Levels, and Infrared Line List for (32)S(16)O2 up to 8000 cm(exp -1)

A purely ab initio potential energy surface (PES) was refined with selected (32)S(16)O2 HITRAN data. Compared to HITRAN, the root-mean-squares error (RMS) error for all J=0-80 rovibrational energy levels computed on the refined PES (denoted Ames-1) is 0.013 cm(exp -1). Combined with a CCSD(T)/aug-cc-pV(Q+d)Z dipole moment surface (DMS), an infrared (IR) line list (denoted Ames-296K) has been computed at 296K and covers up to 8,000 cm(exp -1). Compared to the HITRAN and CDMS databases, the intensity agreement for most vibrational bands is better than 85-90%. Our predictions for (34)S(16)O2 band origins, higher energy (32)S(16)O2 band origins and missing (32)S(16)O2 IR bands have been verified by most recent experiments and available HITRAN data. We conclude that the Ames-1 PES is able to predict (32/34)S(16)O2 band origins below 5500 cm(exp -1) with 0.01-0.03 cm(exp -1) uncertainties, and the Ames-296K line list provides continuous, reliable and accurate IR simulations. The Ka-dependence of both line position and line intensity errors is discussed. The line list will greatly facilitate SO2 IR spectral experimental analysis, as well as elimination of SO2 lines in high-resolution astronomical observations.

Sulfur Dioxide (SO2)↗

Verification of the H2O Linelists with Theoretically Developed Tools

Two basic rules (i.e., the pair identity and the smooth variation rules) resulting from the properties of the energy levels and wave functions of H2O states govern how the spectroscopic parameters vary with the H2O lines within the individually defined groups of lines. With these rules, for those lines involving high j states in the same groups, variations of all their spectroscopic parameters (i.e., the transition frequency, intensity, pressure broadened half-width, pressure-induced shift, and temperature exponent) can be well monitored. Thus, the rules can serve as simple and effective tools to screen the H2O spectroscopic data listed in the HITRAN database and verify the latter's accuracies. By checking violations of the rules occurring among the data within the individual groups, possible errors can be picked up and also possible missing lines in the linelist whose intensities are above the threshold can be identified. We have used these rules to check the accuracies of the spectroscopic parameters and the completeness of the linelists for several important H2O vibrational bands. Based on our results, the accuracy of the line frequencies in HITRAN 2008 is consistent. For the line intensity, we have found that there are a substantial number of lines whose intensity values are questionable. With respect to other parameters, many mistakes have been found. The above claims are consistent with a well known fact that values of these parameters in HITRAN contain larger uncertainties. Furthermore, supplements of the missing line list consisting of line assignments and positions can be developed from the screening results.

spectroscopy↗

Significant Attenuation of Lightly Damped Resonances Using Particle Dampers

When equipment designs must perform in a broad band vibration environment it can be difficult to avoid resonances that affect life and performance. This is especially true when an organization seeks to employ an asset from a heritage design in a new, more demanding vibration environment. Particle dampers may be used to provide significant attenuation of lightly damped resonances to assist with such a deployment of assets by including only a very minor set of modifications. This solution may be easier to implement than more traditional attenuation schemes. Furthermore, the cost in additional weight to the equipment can be very small. Complexity may also be kept to a minimum, because the particle dampers do not require tuning. Attenuating the vibratory response with particle dampers may therefore be simpler (in a set it and forget it kind of way) than tuned mass dampers. The paper will illustrate the use of an "equivalent resonance test jig" that can assist designers in verifying the potential resonance attenuation that may be available to them during the early trade stages of the design. An approach is suggested for transforming observed attenuation in the jig to estimated performance in the actual service design. KEY WORDS: Particle Damper, Performance in Vibration Environment, Damping, Resonance, Attenuation, Mitigation of Vibration Response, Response Estimate, Response Verification.

Smith, Andrew↗

High-Resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons: The Realm of Anharmonicity

We report on an experimental and theoretical investigation of the importance of anharmonicity in the 3 micrometers CH stretching region of Polycyclic Aromatic Hydrocarbon (PAH) molecules. We present mass-resolved, high-resolution spectra of the gas-phase cold ((is) approximately 4K) linear PAH molecules naphthalene, anthracene, and tetracene. The measured IR spectra show a surprisingly high number of strong vibrational bands. For naphthalene, the observed bands are well separated and limited by the rotational contour, revealing the band symmetries. Comparisons are made to the harmonic and anharmonic approaches of the widely used Gaussian software. We also present calculated spectra of these acenes using the computational program SPECTRO, providing anharmonic predictions enhanced with a Fermi-resonance treatment that utilizes intensity redistribution. We demonstrate that the anharmonicity of the investigated acenes is strong, dominated by Fermi resonances between the fundamental and double combination modes, with triple combination bands as possible candidates to resolve remaining discrepancies. The anharmonic spectra as calculated with SPECTRO lead to predictions of the main modes that fall within 0.5% of the experimental frequencies. The implications for the Aromatic Infrared Bands, specifically the 3-m band are discussed.

Astrochemistry↗

Detailed Analysis of Near-IR Water (H2O) Emission in Comet C/2014 Q2 (LOVEJOY) with the GIANO/TNG Spectrograph

We observed the Oort cloud comet C/2014 Q2 (Lovejoy) on 2015 January 31 and February 1 and 2 at a heliocentric distance of 1.3 au and geocentric distance of 0.8 au during its approach to the Sun. Comet Lovejoy was observed with GIANO, the near-infrared high-resolution spectrograph mounted at the Nasmyth-A focus of the TNG (Telescopio Nazionale Galileo) telescope in La Palma, Canary Islands, Spain. We detected strong emissions of radical CN and water, along with many emission features of unidentified origin, across the 1-2.5 micron region. Spectral lines from eight ro-vibrational bands of H2O were detected, six of them for the first time. We quantified the water production rate [Q(H2O), (3.11+/- 0.14) x 10(exp 29)/s] by comparing the calibrated line fluxes with the Goddard full non-resonance cascade fluorescence model for H2O. The production rates of ortho-water [Q(H2O)ORTHO, (2.33+/- 0.11) x 10(exp 29)/s] and para-water [Q(H2O)PARA, (0.87+/-0.21) x 10(exp 29)/s] provide a measure of the ortho-to-para ratio (2.70+/- 0.76)). The confidence limits are not small enough to provide a critical test of the nuclear spin temperature.

Faggi, S.↗

Atmospheric Beacons of Life from Exoplanets Around G and K Stars

The current explosion in detection and characterization of thousands of extrasolar planets from the Kepler mission, the Hubble Space Telescope, and large ground-based telescopes opens a new era in searches for Earth-analog exoplanets with conditions suitable for sustaining life. As more Earth-sized exoplanets are detected in the near future, we will soon have an opportunity to identify habitale worlds. Which atmospheric biosignature gases from habitable planets can be detected with our current capabilities? The detection of the common biosignatures from nitrogen-oxygen rich terrestrial-type exoplanets including molecular oxygen (O2), ozone (O3), water vapor (H2O), carbon dioxide (CO2), nitrous oxide (N2O), and methane (CH4) requires days of integration time with largest space telescopes, and thus are very challenging for current instruments. In this paper we propose to use the powerful emission from rotational-vibrational bands of nitric oxide, hydroxyl and molecular oxygen as signatures of nitrogen, oxygen, and water rich atmospheres of terrestrial type exoplanets "highlighted" by the magnetic activity from young G and K main-sequence stars. The signals from these fundamental chemical prerequisites of life we call atmospheric "beacons of life" create a unique opportunity to perform direct imaging observations of Earth-sized exoplanets with high signal-to-noise and low spectral resolution with the upcoming NASA missions.

exoplanets↗

The Volatile Composition of Comet C/2017 E4 (Lovejoy) before its Disruption, as Revealed by High-Resolution Infrared Spectroscopy with iSHELL at the NASA/IRTF

In 2017 April, we acquired comprehensive high-resolution spectra of newly discovered comet C/2017 E4 (Lovejoy) as it approached perihelion, and before its disintegration. We detected many cometary emission lines in the range (2.8-5.3) μm, in four customized instrument settings (L1-c, L3, Lp1-c, and M1) of iSHELL-the new near-IR high-resolution immersion echelle spectrograph at NASA/IRTF (Maunakea, Hawaii). We identified 12 molecular species: nine primary volatiles (H2O, HCN, NH3, CO, C2H2, C2H6, CH4, CH3OH, H2CO) and three product species (CN, NH2, OH). We detected 85 H2O emission lines from 12 water vibrational bands across L1-c and M1 settings. The many detected water emission lines enabled retrieval of accurate measures for ortho- and para-H2O independently, thereby reducing systematic uncertainty in the derived ortho-para ratio and nuclear spin temperature. Excitation analyses and emission profile analyses were performed for all species, and molecular abundance ratios relative to water are compared with values found for other Oort Cloud comets in our infrared database. Abundance ratios are consistent for most species, with the exception of underabundant methanol and overabundant ammonia in E4.

Faggi, S.↗

Mid and Thermal Infrared Remote Sensing at the Jet Propulsion Laboratory

The mid and thermal infrared (MTIR) for the Earth surface is defined between 3 and 14µm. In the outer solar system, objects are colder and their Planck response shifts towards longer wavelengths. Hence for these objects (e.g. icy moons, polar caps, comets, Europa), the thermal IR definition usually stretches out to 50µm and beyond. Spectroscopy has been a key part of this scientific exploration because of its ability to remotely determine elemental and mineralogical composition. Many key gas species such as methane, ammonia, sulfur, etc. also have vibrational bands which show up in the thermal infrared spectrum above the background response. Over the past few decades, the Jet Propulsion Laboratory has been building up a portfolio of technology to capture the MTIR for various scientific applications. Three recent sensors are briefly reviewed: The airborne Hyperspectral thermal emission spectrometer (HyTES), the ECOsystem Spaceborne Thermal Radiometer Experiment on Space Station (ECOSTRESS) and Mars Climate Sounder (MCS)/DIVINER. Each of these sensors utilize a different technology to provide a remote sensing product based on MTIR science. For example, HyTES is a push-brooming hyperspectral imager which utilizes a large format quantum well infrared photodetector (QWIP). The goal is to transition this to a new complementary barrier infrared photodetector (CBIRD) with a similar long wave cut-off and increased sensitivity. ECOSTRESS is a push-whisk Mercury Cadmium Telluride (MCT) based high speed, multi-band, imager which will eventually observe and characterize plant/vegetation functionality and stress index from the International Space Station (ISS) across the contiguous United States (CONUS). MCS/DIVINER utilizes thermopile technology to capture the thermal emission from the polar caps and shadow regions of the moon. Each sensor utilizes specific JPL technology to capture unique science. similar long wave cut-off and increased sensitivity. ECOSTRESS is a push-whisk Mercury Cadmium Telluride (MCT) based high speed, multi-band, imager which will eventually observe and characterize plant/vegetation functionality and stress index from the International Space Station (ISS) across the contiguous United States (CONUS). MCS/DIVINER utilizes thermopile technology to capture the thermal emission from the polar caps and shadow regions of the moon. Each sensor utilizes specific JPL technology to capture unique science.

Johnson, William R.↗

High-Resolution Spectroscopy of Titan with SOFIA/EXES

We present the first observation of Titan with the high resolution Echelon cross-Echelle Spectrograph(EXES) instrument on the Stratospheric Observatory for Infrared Astronomy (SOFIA, Fig. 1). These show clear detection of multiple spectral lines in the R-branch of the acetylene vibrational band at 13 m. These are compared to similar observations with the ground-based sister instrument TEXES (Texas Echelon cross-Echelle Spectrograph) on the IRTF(Infrared Telescope Facility), showing that EXES will have access to an enlarged spectral range as expected, through reduced atmospheric opacity. In future EXES will be used to complement TEXES for spectral line searches on Titan, geared to detect new molecular species, focusing on spectral regions that are inaccessible from the ground.

Nixon, Conor A.↗

The Volatile Composition of Comet C/2017 E4 (Lovejoy) Before Its Disruption, as Revealed by High-Resolution Infrared Spectroscopy with iSHELL at the NASA-IRTF

In April 2017, we acquired comprehensive high-resolution spectra of newly-discovered comet C/2017 E4 (Lovejoy) as it approached perihelion, and before its disintegration. We detected many cometary emission lines in the (2.8–5.3)μm range, in four customized instrument settings (L1-c, L3, Lp1-cand M1) of iSHELL -the new near-IR high resolution immersion echelle spectrograph at NASA/IRTF (Maunakea, Hawaii). We identified twelve molecular species; nine primary volatiles (H2O, HCN, NH3, CO, C2H2, C2H6, CH4, CH3OH, H2CO) and three product species (CN, NH2,OH). We detected 85H2O emission lines from 12 water vibrational bands across L1-c and M1 settings. The many detected water emission lines enabled retrieval of accurate measures for ortho-and para-H2O independently, thereby reducing systematic uncertainty in the derived ortho-para ratio and nuclear spin temperature. Excitation analyses and emission profile analyses were performed for all species, and molecular abundance ratios relative to water are compared with values found for other Oort Cloud comets in our infrared database. Abundance ratios are consistent for most species, with the exception of under-abundant methanol and over-abundant ammonia in E4.

S. Faggi↗

PAH Products and Processing by Different Energy Sources

Isoviolanthrene (C34H18), a polycyclic aromatic hydrocarbon (PAH) molecule, was studied via matrix isolation in argon and water at 20 K. Infrared spectroscopy was performed in situ where samples were irradiated using ultraviolet light. Experimental spectra were compared to theoretical spectra for vibrational band assignment, determination of the corresponding A-values, and photoproduct identification. Isoviolanthrene was also deposited as a thin film and irradiated with different energy sources: ultraviolet photons (10.2 eV), soft electrons (1.5 keV), protons (1.5 MeV), and He+ particles (1.5 MeV), to understand the effects of different energy sources on a PAH. Anions and cations of soviolanthrene were produced as a result of UV photolysis in an argon matrix. Hydrogenand oxygen-rich aromatic photoproducts were produced by ultraviolet photons when isoviolanthrene was isolated in a water matrix. The irradiated PAH thin films results were dependent on the energy source. Irradiation with ultraviolet photons yielded a broad underlying feature centered at 9.6 μm, while bombardment with soft electrons gave a broad feature centered at 7.7 μm. In the case of proton bombardment, no broad feature was detected, in contrast with He+ bombardment that destroyed most of the isoviolanthrene and produced broad features in the C-Hoop and C–H stretching regions. A comparison of astronomical IR emission observations with our experimental results in the mid-infrared range has revealed a similarity between the observed plateaus and the broad features produced by our experiments.

astrochemistry – infrared: ISM – methods: laborato↗

Ultraviolet Photooxidation of Smectite-Bound Fe(II) and Implications for the Origin of Martian Nontronites

Clay minerals detected with orbital and in situ instruments in ancient Martian terrains constrain Mars' climate and aqueous alteration history. Early in its history, Mars experienced an atmospheric redox change and iron-bearing clay minerals may preserve the effects of that transition. Ferrous smectites, the thermodynamically predicted product of chemical weathering of basalts under anoxic conditions, may have undergone oxidation by exposure to chemical oxidants in the atmosphere or regolith, or by direct photooxidation at the surface. To assess these potential oxidation pathways, ferrous trioctahedral smectites of varying initial iron content were synthesized and subjected to oxidation by ultraviolet (UV) irradiation. Experimental UV irradiation under an anoxic atmosphere equivalent to approximately 7 years of flux on the Martian surface caused partial oxidation of smectite-bound Fe (Fe3+/ΣFe = 16–18%) and octahedral sheet contraction. Metal-OH vibrational bands in visible/near infrared (VNIR) reflectance spectra of oxidized smectites changed in band depth and asymmetry with higher iron content. X-ray diffraction patterns of UV irradiated samples indicate the formation of a mixed di- and trioctahedral smectite or a secondary nontronite phase, possibly on the surfaces of higher iron content smectites. These experiments suggest that UV irradiation is able to oxidize structurally bound iron in smectites without the presence of other chemical oxidants. Photooxidation may have influenced the mineralogy, both syndepositionally and postdepositionally, of Martian alteration assemblages formed near the surface and this process needs not be limited to one part of their formation history. Plain Language Summary: Martian mineral assemblages observed with orbiters and rover instruments allow us to understand the planet's past climate and aqueous activity. Hydrated minerals that contain Fe(II) are of particular interest as they would have been affected by the early atmosphere becoming more oxidizing overtime, changing the structural iron into Fe(III). In this study, we synthesized Fe(II) smectites with varying iron content and irradiated them with an ultraviolet (UV) light source to test whether they could be photooxidized. Iron in the smectite minerals was incompletely oxidized by UV radiation after being exposed for the equivalent of approximately 7 years of exposure on the early Mars surface. The smectites with higher iron content showed more changes with photooxidation in their visible/near infrared spectra as well as in their X-ray diffraction patterns, two datasets collected by instruments on currently active Martian missions. These results suggest that UV photooxidation is a plausible contributor to the mineralogy and redox state of clay mineral assemblages observed at the Martian surface.

V. B. Rivera Banuchi↗