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At least 1,081 records · Page 60

Chemical Evolution in the Interstellar Medium: From Astrochemistry to Astrobiology

Great strides have been made in our understanding of interstellar material thanks to advances in infrared astronomy and laboratory astrophysics. Ionized polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by earlier astrochemical standards, are widespread and very abundant throughout much of the Universe. In cold molecular clouds, the birthplace of planets and stars, interstellar molecules freeze onto dust and ice particles forming mixed molecular ices dominated by simple species such as water, methanol, ammonia, and carbon monoxide. Within these clouds, and especially in the vicinity of star and planet forming regions, these ices and PAHs are processed by ultraviolet light and cosmic rays forming hundreds of far more complex species, some of biogenic interest. Eventually, these are delivered to primordial planets by comets and meteorites. Astrochemical evolution, highlights of this field from a chemist's perspective, and the astronomer's infrared toolbox will be reviewed.

Allamandola, Louis J.↗

Irradiation of FeS: Implications for the Lifecycle of Sulfur in the Interstellar Medium and Presolar FeS Grains

Fe(Ni) sulfides are ubiquitous in chondritic meteorites and cometary samples where they are the dominant host of sulfur. Despite their abundance in these early solar system materials, their presence in interstellar and circumstellar environments is poorly understood. Fe-sulfides have been reported from astronomical observations of pre- and post-main sequence stars [1, 2] and occur as inclusions in bonafide circumstellar silicate grains [3, 4]. In cold, dense molecular cloud (MC) environments, sulfur is highly depleted from the gas phase [e.g. 5], yet observations of sulfur-bearing molecules in dense cores find a total abundance that is only a small fraction of the sulfur seen in diffuse regions [6], therefore the bulk of the depletion must reside in an abundant unobserved phase. In stark contrast, sulfur is essentially undepleted from the gas phase in the diffuse interstellar medium (ISM) [7-9], indicating that little sulfur is incorporated into solid grains in this environment. This is a rather puzzling observation unless Fe-sulfides are not produced in significant quantities in stellar outflows, or their lifetime in the ISM is very short due to rapid destruction. The main destruction mechanism is sputtering due to supernova shocks in the warm, diffuse ISM [10]. This process involves the reduction of Fe-sulfide with the production of Fe metal as a by-product and returning S to the gas phase. In order to test this hypothesis, we irradiated FeS and analyzed the resulting material using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM).

Keller, Lindsay P.↗

Isotopic Fractionation in Primitive Material: Quantifying the Contribution of Interstellar Chemistry

Anomalously fractionated isotopic material is found in many primitive Solar System objects, such as meteorites and comets. It is thought, in some cases, to trace interstellar matter that was incorporated into the Solar Nebula without undergoing significant processing. We will present the results of models of the nitrogen, oxygen, and carbon fractionation chemistry in dense molecular clouds, particularly in cores where substantial freeze-out of molecules on to dust has occurred. The range of fractionation ratios expected in different interstellar molecules will be discussed and compared to the ratios measured in molecular clouds, comets and meteoritic material. These models make several predictions that can be tested in the near future by molecular line observations, particularly with ALMA.

Charnley, Steven↗

Isotopic Fractionation in Comets: Quantifying the Contribution of Interstellar Chemistry

Anomalously fractionated isotopic material is found in many primitive Solar System objects, such as meteorites and comets. It is thought, in some cases, to trace interstellar matter that was incorporated into the Solar Nebula without undergoing significant processing. We will present the results of models of the nitrogen, oxygen, and carbon fractionation chemistry in dense molecular clouds, particularly in cares where substantial freeze-taut of molecules on to dust has occurred. The range of fractionation ratios expected in different interstellar molecules will be discussed and compared to the ratios measured in molecular clouds, comets and meteoritic material. These models make several predictions that can be tested in the near future by molecular line observations, particularly with the GBT.

Charnley, Steven↗

Searching for Cost-Optimized Interstellar Beacons

What would SETI beacon transmitters be like if built by civilizations that had a variety of motives but cared about cost? In a companion paper, we presented how, for fixed power density in the far field, a cost-optimum interstellar beacon system could be built. Here, we consider how we should search for a beacon if it were produced by a civilization similar to ours. High-power transmitters could be built for a wide variety of motives other than the need for two-way communication, this would include beacons built to be seen over thousands of light-years. Extraterrestrial beacon builders would likely have to contend with economic pressures just as their terrestrial counterparts do. Cost, spectral lines near 1GHz, and interstellar scintillation favor radiating frequencies substantially above the classic "water hole." Therefore, the transmission strategy for a distant, cost-conscious beacon would be a rapid scan of the galactic plane with the intent to cover the angular space. Such pulses would be infrequent events for the receiver. Such beacons built by distant, advanced, wealthy societies would have very different characteristics from what SETI researchers seek. Future searches should pay special attention to areas along the galactic disk where SETI searches have seen coherent signals that have not recurred on the limited listening time intervals we have used. We will need to wait for recurring events that may arrive in intermittent bursts. Several new SETI search strategies have emerged from these ideas. We propose a new test for beacons that is based on the Life Plane hypotheses.

Benford, Gregory↗

Feasibility Study of Interstellar Missions Using Laser Sail Probes Ranging in Size from the Nano to the Macro

This paper presents the analysis examining the feasibility of interstellar travel using laser sail probes ranging in size from the nano to the macro. The relativistic differential equations of motion for a laser sail are set up and solved using the Pasic Method. The limitations of the analysis are presented and discussed. The requirements for the laser system are examined, including the thermal analysis of the laser sails. Black holes, plasma fields, atmospheric collisions and sun light are several methods discussed to enable the deceleration of the interstellar probe. A number of novel mission scenarios are presented including the embryonic transport of plant life as a precursor to the arrival of space colonies

Malroy, Eric T.↗

The Search for Interstellar Sulfide Grains

The lifecycle of sulfur in the galaxy is poorly understood. Fe-sulfide grains are abundant in early solar system materials (e.g. meteorites and comets) and S is highly depleted from the gas phase in cold, dense molecular cloud environments. In stark contrast, sulfur is essentially undepleted from the gas phase in the diffuse interstellar medium, indicating that little sulfur is incorporated into solid grains in this environment. It is widely believed that sulfur is not a component of interstellar dust grains. This is a rather puzzling observation unless Fe-sulfides are not produced in significant quantities in stellar outflows, or their lifetime in the ISM is very short due to rapid destruction. Fe sulfide grains are ubiquitous in cometary samples where they are the dominant host of sulfur. The Fe-sulfides (primarily pyrrhotite; Fe(1-x)S) are common, both as discrete 0.5-10 micron-sized grains and as fine (5-10 nm) nanophase inclusions within amorphous silicate grains. Cometary dust particles contain high abundances of well-preserved presolar silicates and organic matter and we have suggested that they should contain presolar sulfides as well. This hypothesis is supported by the observation of abundant Fe-sulfides grains in dust around pre- and post-main sequence stars inferred from astronomical spectra showing a broad 23 micron IR feature due to FeS. Fe-sulfide grains also occur as inclusions in bona fide circumstellar amorphous silicate grains and as inclusions within deuterium-rich organic matter in cometary dust samples. Our irradiation experiments show that FeS is far more resistant to radiation damage than silicates. Consequently, we expect that Fe sulfide stardust should be as abundant as silicate stardust in solar system materials.

Keller, Lindsay P.↗

Constraining the Origin of Impact Craters on Al Foils from the Stardust Interstellar Dust Collector

Preliminary examination (PE) of the aerogel tiles and Al foils from the Stardust Interstellar Dust Collector has revealed multiple impact features. Some are most likely due to primary impacts of interstellar dust (ISD) grains, and others are associated with secondary impacts of spacecraft debris, and possibly primary impacts of interplanetary dust particles (IDPs) [1, 2]. The current focus of the PE effort is on constraining the origin of the individual impact features so that definitive results from the first direct laboratory analysis of contemporary ISD can be reported. Because crater morphology depends on impacting particle shape and composition, in addition to the angle and direction of impact, unique particle trajectories are not easily determined. However, elemental analysis of the crater residues can distinguish real cosmic dust from the spacecraft debris, due to the low cosmic abundance of many of the elements in the spacecraft materials. We present here results from the elemental analysis of 24 craters and discuss the possible origins of 4 that are identified as candidate ISD impacts

Stroud, Rhonda M.↗

Identification of Crystalline Material in Two Interstellar Dust Candidates from the Stardust Mission

NASA's interstellar collector from the Stardust mission captured several particles that are now thought to be of interstellar origin. We analyzed two of these via nanodiffraction at the European Synchrotron Radiation Facility (ESRF) and found them to contain crystalline components. The unit cell of the crystalline material is determined from the diffraction patterns and the most likely mineral components are identified as olivine and spinel.

Gainsforth, Zack↗

Isotope Fractionation in the Interstellar Medium

Anomalously fractionated isotopic material is found in many primitive Solar System objects, such as meteorites and comets. It is thought, in some cases, to trace interstellar matter that was incorporated into the Solar Nebula without undergoing significant processing. We will present the results of models of the nitrogen, oxygen, and carbon fractionation chemistry in dense molecular clouds, particularly in cores where substantial freeze-out of molecules on to dust has occurred. The range of fractionation ratios expected in different interstellar molecules will be discussed and compared to the ratios measured in molecular clouds, comets and meteoritic material. These models make several predictions that can be tested in the near future by molecular line observations, particularly with ALMA.

Charnley, Steven↗

On the Formation of Interstellar Water Ice: Constraints from a Search for Hydrogen Peroxide Ice in Molecular Clouds

Recent surface chemistry experiments have shown that the hydrogenation of molecular oxygen on interstellar dust grains is a plausible formation mechanism, via hydrogen peroxide (H2O2), for the production of water (H2O) ice mantles in the dense interstellar medium. Theoretical chemistry models also predict the formation of a significant abundance of H2O2 ice in grain mantles by this route. At their upper limits, the predicted and experimental abundances are sufficiently high that H2O2 should be detectable in molecular cloud ice spectra. To investigate this further, laboratory spectra have been obtained for H2O2/H2O ice films between 2.5 and 200 micron, from 10 to 180 K, containing 3%, 30%, and 97% H2O2 ice. Integrated absorbances for all the absorption features in low-temperature H2O2 ice have been derived from these spectra. For identifying H2O2 ice, the key results are the presence of unique features near 3.5, 7.0, and 11.3 micron. Comparing the laboratory spectra with the spectra of a group of 24 protostars and field stars, all of which have strong H2O ice absorption bands, no absorption features are found that can definitely be identified with H2O2 ice. In the absence of definite H2O2 features, the H2O2 abundance is constrained by its possible contribution to the weak absorption feature near 3.47 micron found on the long-wavelength wing of the 3 micron H2O ice band. This gives an average upper limit for H2O2, as a percentage of H2O, of 9% +/- 4%. This is a strong constraint on parameters for surface chemistry experiments and dense cloud chemistry models.

Smith, R. G.↗

Formation of Benzene in the Interstellar Medium

Polycyclic aromatic hydrocarbons and related species have been suggested to play a key role in the astrochemical evolution of the interstellar medium, but the formation mechanism of even their simplest building block-the aromatic benzene molecule-has remained elusive for decades. Here we demonstrate in crossed molecular beam experiments combined with electronic structure and statistical calculations that benzene (C6H6) can be synthesized via the barrierless, exoergic reaction of the ethynyl radical and 1,3- butadiene, C2H + H2CCHCHCH2 --> C6H6, + H, under single collision conditions. This reaction portrays the simplest representative of a reaction class in which aromatic molecules with a benzene core can be formed from acyclic precursors via barrierless reactions of ethynyl radicals with substituted 1,3-butadlene molecules. Unique gas-grain astrochemical models imply that this low-temperature route controls the synthesis of the very first aromatic ring from acyclic precursors in cold molecular clouds, such as in the Taurus Molecular Cloud. Rapid, subsequent barrierless reactions of benzene with ethynyl radicals can lead to naphthalene-like structures thus effectively propagating the ethynyl-radical mediated formation of aromatic molecules in the interstellar medium.

Jones, Brant M.↗

Isotopic Anomalies in Primitive Solar System Matter: Spin-State-Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15. This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar nebula, Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotopic enrichments measured in carbonaceous meteorites. However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores. We also show that while the nitriles, HCN and HNC, contain the greatest N=15 enrichment, this is not expected to correlate with extreme D enrichment. These calculations therefore support the view that solar system N-15 and D isotopic anomalies have an interstellar heritage. We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

Wirstrom, Eva S.↗

Submillimeter Measurements of Photolysis Products in Interstellar Ice Analogs: A New Experimental Technique

Over 150 molecular species have been confirmed in space, primarily by their rotational spectra at millimeter/submillimeter wavelengths, which yield an unambiguous identification. Many of the known interstellar organic molecules cannot be explained by gas-phase chemistry. It is now presumed that they are produced by surface reactions of the simple ices and/or grains observed and released into the gas phase by sublimation, sputtering, etc. Additionally, the chemical complexity found in meteorites and samples returned from comets far surpasses that of the remote detections for the interstellar medium (ISM), comets, and planetary atmospheres. Laboratory simulations of interstellar/cometary ices have found, from the analysis of the remnant residue of the warmed laboratory sample, that such molecules are readily formed; however, it has yet to be determined if they are formed during the warm phase or within the ice during processing. Most analysis of the ice during processing reveals molecular changes, though the exact quantities and species formed are highly uncertain with current techniques due to overwhelming features of simple ices. Remote sensing with high resolution spectroscopy is currently the only method to detect trace species in the ISM and the primary method for comets and icy bodies in the Solar System due to limitations of sample return. We have recently designed an experiment to simulate interstellar/cometary/planetary ices and detect trace species employing the same techniques used for remote observations. Preliminary results will be presented.

Milam, Stefanie N.↗

Isotopic Anomalies in Primitive Solar System Matter: Spin-State Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15, This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar core. Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotop c enrichments measured in carbonaceous meteorites, However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores, We also show that while the nitriles, HCN and HNC, contain the greatest N-15 enrichment, this is not expected to correlate with extreme D emichment. These calculations therefore support the view that Solar System N-15 and D isotopic anomalies have an interstellar heritage, We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

Wirstrom, Eva S.↗

The Possible Interstellar Anion CH2CN-: Spectroscopic Constants, Vibrational Frequencies, and Other Considerations

The A 1B1 <-1A0 excitation into the dipole-bound state of the cyanomethyl anion (CH2CN􀀀) has been hypothesized as the carrier for one di use interstellar band. However, this particular molecular system has not been detected in the interstellar medium even though the related cyanomethyl radical and the isoelectronic ketenimine molecule have been found. In this study we are employing the use of proven quartic force elds and second-order vibrational perturbation theory to compute accurate spectroscopic constants and fundamental vibrational frequencies for ~X 1A0 CH2CN􀀀 in order to assist in laboratory studies and astronomical observations. Keywords: Astrochemistry, ISM: molecular anions, Quartic force elds, Rotational constants, Vibrational frequencies

Astrochemistry↗

Laboratory Determination of the Infrared Band Strengths of Pyrene Frozen in Water Ice: Implications for the Composition of Interstellar Ices

Broad infrared emission features (e.g., at 3.3, 6.2, 7.7, 8.6, and 11.3 micrometers) from the gas phase interstellar medium have long been attributed to polycyclic aromatic hydrocarbons (PAHs). A significant portion (10 to 20%) of the Milky Way's carbon reservoir is locked in PAH molecules, which makes their characterization integral to our understanding of astrochemistry. In molecular clouds and the dense envelopes and disks of young stellar objects (YSOs), PAHs are expected to be frozen in the icy mantles of dust grains where they should reveal themselves through infrared absorption. To facilitate the search for frozen interstellar PAHs, laboratory experiments were conducted to determine the positions and strengths of the bands of pyrene mixed with H2O and deuterium oxide ices. The deuterium oxide mixtures are used to measure pyrene bands that are masked by the strong bands of H2O, leading to the first laboratory determination of the band strength for the CH stretching mode of pyrene in water ice near 3.25 micrometers. Our infrared band strengths were normalized to experimentally determined ultraviolet (UV) band strengths, and we find that they are generally approximately 50% larger than those reported by Bouwman et al. (2011) based on theoretical strengths. These improved band strengths were used to reexamine YSO spectra published by Boogert et al. (2008) to estimate the contribution of frozen PAHs to absorption in the 5 to 8 micrometer spectral region, taking into account the strength of the 3.25 micrometer CH stretching mode. It is found that frozen neutral PAHs contain 5 to 9% of the cosmic carbon budget, and account for 2 to 9% of the unidentified absorption in the 5 to 8 micrometer region.

polycyclic aromatic hydrocarbons (PAHs)↗

On Ion Clusters in the Interstellar Gas

In a recent paper V.I. Krassovsky (1958) predicts the occurrence of clusters of large numbers of atoms and molecules around ions in the interstellar gas. He then proposes a number of physicochemical processes that would be considerably enhanced by the high particle density in such clusters. In particular, he suggests that absorption by negative ions formed in the clusters would account for the interstellar extinction without any necessity for the presence of grains. Because of the important consequences that ion clusters could have, it is necessary to examine their occurrence more fully. This note re-examines the formation of ion clusters in space and shows that even ion-molecule pairs are essentially non-existent. Ion clusters have been considered by Bloom and Margenau (1952) from the same point of view as that used by Krassovsky, whose basic reference (Joffe and Semenov 1933) unfortunately is not available. A different approach has been used by Eyring, Hirschfelder, and Taylor (1936) following the methods of chemical equilibrium. Both the references cited here enable one to conclude that clustering is negligible. Therefore, the treatment of Eyring et al. is more appropriate than the method of Bloom and Margenau, which depends on the statistical equilibrium of an atmosphere in a force field.

Donn, Bertram↗