Engineering topics

Bernstein, M. P.

Publications and source records attributed to Bernstein, M. P..

16 records

NASA NTRS2006

The Location of the CO2, Fundamental in Clathrate Hydrates and its Application to Infrared Spectra of Icy Solar System Objects

CO2 is present on the surface of many Solar System objects, but not always as a segregated, pure ice. In pure CO2-ice, the fundamental absorption is located near 4.268 micron (2343.3 wavenumbers). However, on several objects, the CO2 fundamental is shifted to higher frequency. This shift may be produced by CO2 gas trapped in another material, or adsorbed onto minerals. We have seen that a mixture of H2O, CH3OH4 and CO2 forms a type II clathrate when heated to 125 K and produces a CO2 fundamental near 4.26 micron. The exact location of the feature is strongly dependent on the initial ratio of the three components. We are currently exploring various starting ratios relevant to the Solar System to determine the minimum amount of CH3OH needed to convert all of the CO2 to the clathrate, i.e. eliminate the splitting of the CO2 fundamental. We are testing the stability of the clathrate to thermal processing and UV photolysis, and documenting the changes seen in the spectra in the wavelength range from 1-5 micron. We acknowledge financial support from the Origins of Solar Systems Program, the Planetary Geology and Geophysics and the NASA Postdoctoral Program.

Sandford, S. A.↗

NASA NTRS2006

Near Infrared Spectra of H2O/HCN Mixtures

Cassini's VIMS has already returned exciting results interpreting spectra of Saturn's icy satellites. The discovery of unidentified features possibly due to CN compounds inspired the work reported here. We wanted to test HCN as a possibility for explaining these features, and also explore how the features of HCN change when mixed with H2O. We have previously noted that mixing H20 and CO2 produces new spectral features and that those features change with temperature and mixing ratio.

Mastrapa, R. M.↗

NASA NTRS2005

UV IRRADIATION OF AROMATIC NITROGEN HETEROCYCLES IN INTERSTELLAR ICE ANALOGS

Here, we present information on the properties of the ANH quinoline frozen in interstellar water-ice analogs. Quinoline is a two-ring compound structurally analogous to the PAH naphthalene. In this work, binary mixtures of water and quinoline were frozen to create interstellar ice analogs, which were then subjected to ultraviolet photolysis. We will present the infrared spectra of the resulting ices at various temperatures, as well as chromatographic analysis of the residues remaining upon warm-up of these ices to room temperature.

Elsila, J. E.↗

NASA NTRS2005

The Mid-Infrared Absorption Spectra of Neutral PAHs in Dense Interstellar Clouds

Polycyclic aromatic hydrocarbons (PAHs) are common throughout the universe and are expected to be present in dense interstellar clouds. In these environments, some P.4Hs may be present in the gas phase, but most should be frozen into ice mantles or adsorbed onto dust grains and their spectral features are expected to be seen in absorption. Here we extend our previous work on the infrared spectral properties of the small PAH naphthalene (C10H8) in several media to include the full mid-infrared laboratory spectra of 11 other PAHs and related aromatic species frozen in H2O ices. These include the molecules 1,2-dihydronaphthalene, anthracene, 9,1O-dihydroanthracene, phenanthrene, pyrene, benzo[e]pyrene, perylene, benzo(k)fluoranthene, pentacene, benzo[ghi]perylene, and coronene. These results demonstrate that PAHs and related molecules, as a class, show the same spectral behaviors as naphthalene when incorporated into H2O-rich matrices. When compared to the spectra of these same molecules isolated in inert matrices (e.g., Ar or N2), the absorption bands produced when they are frozen in H2O matrices are broader (factors of 3-10), show small position shifts in either direction (usually < 4/cm, always < 10/cm), and show variable changes in relative band strengths (typically factors of 1-3). There is no evidence of systematic increases or decreases in the absolute strengths of the bands of these molecules when they are incorporated in H2O matrices. In H2O-rich ices, their absorption bands are relatively insensitive to concentration over the range of 10 < H2O/PAH < 200): The absorption bands of these molecules are also insensitive to temperature over the 10 K < T < 125 K range, although the spectra can show dramatic changes as the ices are warmed through the temperature range in which amorphous H2O ice converts to its cubic and hexagonal crystalline forms (T > 125 Kj. Given the small observed band shifts cause by H2O, the current database of spectra from Ar matrix-isolated neutral PAHs and related molecules should be useful for the search for these species in dense clouds on the basis of observed absorption band positions. Furthermore, these data permit determination of column densities to better than a factor of 3 for PAHs in dense clouds. Column density determination of detected aromatics to better than a factor of 3 will, however, require good knowledge about the nature of the matrix in which the PAH is embedded and laboratory studies of relevant samples.

Bernstein, M. P.↗

NASA NTRS2004

Laboratory Infrared Spectra of Polycyclic Aromatic Nitrogen Heterocycles: Quinoline, and Phenanthridine in Solid Argon and H2O

Polycyclic aromatic hydrocarbons (PAHs) are common throughout the universe. Their detection and identification are based on telescopic infrared (IR) spectra compared with laboratory data. Polycyclic Aromatic Nitrogen Heterocycles (PANHs) are heterocyclic aromatics i.e., PAHs with carbon atoms replaced by a nitrogen atom. These molecules should be present in the interstellar medium, but have received relatively little attention. We present mid-IR spectra of two PANHs, quinoline (C9H7N), and phenanthridine (C13H9N) isolated in solid argon and frozen in solid H2O at 12 K, conditions yielding data directly comparable to astronomical observations. In contrast to simple PAHs, that do not interact strongly with solid H2O, the nitrogen atoms in PANHs are potentially capable of hydrogen bonding with H2O. Whereas the IR spectrum of phenanthridine in H2O is similar to that of the same compound isolated in an argon matrix, quinoline absorptions shift up to 16 cm(sup -1) (0.072 mm) between argon and H2O. Thus, astronomers will not always be able to rely on IR band positions of matrix isolated PANHs to correctly interpret the absorptions of PANHs frozen in H2O ice grains. Furthermore, our data suggest that relative band areas also vary, so determining column densities to better than a factor of 3 will require knowledge of the matrix in which the PANH is embedded and laboratory studies of relevant samples.

Bernstein, M. P.↗

NASA NTRS2003

Formation and Survival of Amino Acids in Space

The detection of deuterium enrichments in meteoritic hydroxy and amino acids demonstrates that there is a connection between organic material in the interstellar medium and in primitive meteorites. It has generally been assumed that such molecules formed via reactions of small deuterium enriched insterstellar precursors in liquid water on a large asteroidal or cometary parent body. We have recently show that the W photolysis of interstellar/presolar ices can produce the amino acids alanine, serine, and glycine, as well as hydroxy acids, and glycerol, all of which have been extracted from the Murchison meteorite. Thus, some of the probiologically interesting organic compounds, compounds found in meteorites may have formed in presolar ice and have not solely been a product of parent body liquid water chemistry. We will report on our isotopic labeling studies of the mechanism of formation of these interesting compounds, and on astrophysically relevant kinetic studies UV photodecomposition of amino acid precursors in the solid state. This is our first year of exobiology funding on this project.

Bernstein, M. P.↗

NASA NTRS2003

Spectra and Photochemistry of Relevance to Icy Outer Solar System Objects

The Astrochemistry Lab at NASA Ames (www.astrochem.org) has an interest in the organic photochemistry of extraterrestrial ices, having traditionally performed experiments under interstellar conditions. We have recently embarked on projects for PG\&G to measure spectra and elucidate the photochemistry of ices relevant to outer Solar System objects. 1) We will report on the determination of real and imaginary indicies of refraction of H2O and N2 dominated ices containing simple, common, extraterrestrial molecules such as NH3, HCN, formaldehyde, \& methanol. 2) We will compare and contrast the photochemistry of H2O ices containing organic molecules at 100 K with previously reported work at 15 K.

Bernstein, M. P.↗

NASA NTRS2003

Formation and Survival of Amino Acids in Space

The detection of deuterium enrichments in meteoritic hydroxy and amino acids demonstrates that there is a connection between organic material in the interstellar medium and in piimitive meteorites. It has generally been assumed that such molecules formed via reactions of small deuterium enriched insterstellar precursors in liquid water on a large asteroidal or cometary parent body. We have recently show that the W photolysis of interstellar/presolar ices can produce the amino acids alanine, serine, and glycine, as well as hydroxy acids, and glycerol, all of which have been extracted from the Murchison meteorite. Thus, some of the probiologically interesting organic compounds compounds found in meteorites may have formed in presolar ice and have not solely been a product of parent body liquid water chemistry. We will report on our isotopic labeling studies of the mechanism of formation of these inteiesting compounds, and on astrophysically relevant kinetic studies UV photo-decomposition of amino acid precursors in the solid state. This is our first year of exobiology funding on this project.

Bernstein, M. P.↗

NASA NTRS2002

The Laboratory Production of Complex Organic Molecules in Simulated Interstellar Ices

Much of the volatiles in interstellar dense clouds exist in ices surrounding dust grains. Their low temperatures preclude most chemical reactions, but ionizing radiation can drive reactions that produce a suite of new species, many of which are complex organics. The Astrochemistry Lab at NASA Ames studies the UV radiation processing of interstellar ice analogs to better identify the resulting products and establish links between interstellar chemistry, the organics in meteorites, and the origin of life on Earth. Once identified, the spectral properties of the products can be quantified to assist with the search for these species in space. Of particular interest are findings that UV irradiation of interstellar ice analogs produces molecules of importance in current living organisms, including quinones, amphiphiles, and amino acids.

Dworkin, J. P.↗

NASA NTRS2002

The Production of Amino Acids in Interstellar Ices: Implications for Meteoritic Organics

Indigenous amino acids have been detected in a number of meteorites, over 70 in the Murchison meteorite alone. It has been generally accepted that the amino acids in meteorites formed in liquid water on an asteroid or comet parent-body. However, the water in the Murchison meteorite, for example, was depleted of deuterium, making the distribution of deuterium in organic acids in Murchison difficult to explain. Similarly, occasional but consistent meteoritic biases for non-terrestrial L amino acids cannot be reasonably rationalized by liquid water parent-body reactions. We will present the results of a laboratory demonstration showing that the amino acids glycine, alanine, and serine should result from the UV (ultraviolet) photolysis of interstellar ice grains. This suggests that some meteoritic amino acids may be the result of interstellar ice photochemistry, rather than having formed by reactions in liquid water. We will describe some of the potential implications of these findings for the organic materials found in primitive meteorites, in particular how interstellar ice synthesis might more easily accommodate the presence and distribution of deuterium, and the meteoritic bias for L amino acids.

Sandford, A.↗

NASA NTRS2000

Deuterium enrichment of polycyclic aromatic hydrocarbons by photochemically induced exchange with deuterium-rich cosmic ices

The polycyclic aromatic hydrocarbon (PAH) coronene (C24H12) frozen in D2O ice in a ratio of less than 1 part in 500 rapidly exchanges its hydrogen atoms with the deuterium in the ice at interstellar temperatures and pressures when exposed to ultraviolet radiation. Exchange occurs via three different chemical processes: D atom addition, D atom exchange at oxidized edge sites, and D atom exchange at aromatic edge sites. Observed exchange rates for coronene (C24H12)-D2O and d12-coronene (C24D12)-H2O isotopic substitution experiments show that PAHs in interstellar ices could easily attain the D/H levels observed in meteorites. These results may have important consequences for the abundance of deuterium observed in aromatic materials in the interstellar medium and in meteorites. These exchange mechanisms produce deuteration in characteristic molecular locations on the PAHs that may distinguish them from previously postulated processes for D enrichment of PAHs.

NASA Center ARC↗

NASA NTRS1999

Variations in the strength of the infrared forbidden 2328.2 cm-1 fundamental of solid N2 in binary mixtures

We present the 2335-2325 cm-1 infrared spectra and band positions, profiles and strengths (A values) of solid nitrogen and binary mixtures of N2 with other molecules at 12 K. The data demonstrate that the strength of the infrared forbidden N2 fundamental near 2328 cm-1 is moderately enhanced in the presence of NH3, strongly enhanced in the presence of H2O and very strongly enhanced (by over a factor of 1000) in the presence of CO2, but is not significantly affected by CO, CH4, or O2. The mechanisms for the enhancements in N2-NH3 and N2-H2O mixtures are fundamentally different from those proposed for N2-CO2 mixtures. In the first case, interactions involving hydrogen-bonding are likely the cause. In the latter, a resonant exchange between the N2 stretching fundamental and the 18O = 12C asymmetric stretch of 18O12C16O is indicated. The implications of these results for several astrophysical issues are briefly discussed.

NASA Discipline Exobiology↗

NASA NTRS1999

The interstellar 4.62 micron band

We present new 4.5-5.1 micron (2210-1970 cm-1) spectra of embedded protostars, W33 A, AFGL 961 E, AFGL 2136, NGC 7538 IRS 9, and Mon R2 IRS 2, which contain a broad absorption feature located near 4.62 micron (2165 cm-1), commonly referred to in the literature as the "X-C triple bond N" band. The observed peak positions and widths of the interstellar band agree to within 2.5 cm-1 and 5 cm-1, respectively. The strengths of the interstellar 4.62 micrometers band and the ice absorption features in these spectra are not correlated, which suggests a diversity of environmental conditions for the ices we are observing. We explore several possible carriers of the interstellar band and review possible production pathways through far-ultraviolet photolysis (FUV), ion bombardment of interstellar ice analog mixtures, and acid-base reactions. Good fits to the interstellar spectra are obtained with an organic residue produced through ion bombardment of nitrogen-containing ices or with the OCN- ion produced either through acid-base reactions or FUV photolysis of NH3-containing ices.

NASA Center ARC↗

NASA NTRS1999

UV irradiation of polycyclic aromatic hydrocarbons in ices: production of alcohols, quinones, and ethers

Polycyclic aromatic hydrocarbons (PAHs) in water ice were exposed to ultraviolet (UV) radiation under astrophysical conditions, and the products were analyzed by infrared spectroscopy and mass spectrometry. Peripheral carbon atoms were oxidized, producing aromatic alcohols, ketones, and ethers, and reduced, producing partially hydrogenated aromatic hydrocarbons, molecules that account for the interstellar 3.4-micrometer emission feature. These classes of compounds are all present in carbonaceous meteorites. Hydrogen and deuterium atoms exchange readily between the PAHs and the ice, which may explain the deuterium enrichments found in certain meteoritic molecules. This work has important implications for extraterrestrial organics in biogenesis.

NASA Center ARC↗

NASA NTRS1997

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↗

NASA NTRS1996

The Composition of Planetesimal 5145 Pholus

We present a new spectrum of 5145 Pholus between 1.15 and 2.4 microns. We model this, and the previously published (0.4-1.0 microns) spectrum, using Hapke scattering theory. The 2.04 micron band of H2O ice is seen in absorption, as well as a strong band at 2.27 Am, interpreted as frozen methanol and/or the methanol photo product hexamethylenetetramine (HMT). The presence of small molecules is indicative of a chemically primitive surface, since heating removes the light hydrocarbons in favor of macromolecular carbon typically found in carbonaceous meteorites. The unusually red slope of Pholus' spectrum is matched by fine grains of Titan tholin, as found previously. Object 1993 HA2, which has an orbit similar to that of 5145 Pholus, is similarly red, but there are as yet no observations of absorption bands in its spectrum. We present a model for the composite spectrum of all spectroscopic and photometric data available for 5145 Pholus and conclude that this is a primitive object which has yet to be substantially processed by solar heat.

Cruikshank, D. P.↗