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Angular motion of a PAH molecule in interstellar environment

Polycyclic aromatic hydrocarbon (PAH) molecules have recently been proposed as an important and hitherto undetected component of the Interstellar Medium (ISM). The theory was based on an explanation of the Unidentified IR Emission Bands by Leger et al. It has already led to a verified prediction on extended galactic and extragalactic emissions measured by IRAS, or by a recent balloon borne experiment. The physics that rules the motion of such molecules in the ISM was studied, taking into account their coupling with the ambient gas, the radiation field (absorption and emission) and the static magnetic field. This is important for many implications of the PAH theory such as the radio emission by these molecules or the expected polarization of their IR emission. A reflection nebulae is considered where the situation is rather well known. Every day life of a mean PAH molecule in such a region is as follows: every 3 hrs a UV photon is absorbed heating the molecule to a thousand degs; the temperature decay due to cooling by IR emission follows then within a few seconds. A collision with a molecule of gas occurs typically once a week, while an H atom is ejected or captured at the same rate. A typical cooling cycle after a heat impulse is given. The PAH molecules studied as representative of the family has typically 50 atoms, a radius of 4.5 A, is circular and has a molecular mass of M = 300; its permanent dipole moment is 3 Debye.

Rouan, D.↗

Electronic spectroscopy of PAHs and PAH derivatives in supersonic jet

Polycyclic Aromatic Hydrocarbon (PAHs) molecules are attracting much attention in the astrophysical and astrochemical communities because of their ubiquitous presence in space due to their ability to survive in the harsh environmental conditions of the interstellar medium(ISM). The objective of this work is to provide gas phase, high-resolution spectroscopic data on the electronic and vibronic transitions of PAHs and their nitrogenated derivatives measured in astrophysically relevant conditions.

CRDS↗

CO and [C ii] line emission of molecular clouds: the impact of stellar feedback and non-equilibrium chemistry

We analyse synthetic 12 CO, 13 CO, and [C ii] emission maps of molecular cloud (MC) simulations from the SILCC-Zoom project. We present radiation, magnetohydrodynamic zoom-in simulations of individual clouds, both with and without radiative stellar feedback, forming in a turbulent multiphase interstellar medium following on-the-fly the evolution of e.g. H 2 , CO, and C + . We introduce a novel post-processing routine based on cloudy which accounts for higher ionization states of carbon due to stellar radiation in H ii regions. Synthetic emission maps of [C ii] in and around feedback bubbles show that the bubbles are largely devoid of [C ii], as recently found in observations, which we attribute to the further ionization of C+ into C 2+ . For both 12 CO and 13 CO, the cloud-averaged luminosity ratio, $L_\rm {CO}/L_\rm {[C\, \small {II}]}$, can neither be used as a reliable measure of the H 2 mass fraction nor of the evolutionary stage of the clouds. We note a relation between the $I_\rm {CO}/I_\rm {[C\, \small {II}]}$ intensity ratio and the H 2 mass fraction for individual pixels of our synthetic maps. The scatter, however, is too large to reliably infer the H 2 mass fraction. Finally, the assumption of chemical equilibrium overestimates H2 and CO masses by up to 150 and 50 per cent, respectively, and $L_\rm {CO}$ by up to 60 per cent. The masses of H and C + would be underestimated by 65 and 30 per cent, respectively, and $L_\rm {[C\, \small {II}]}$ by up to 35 per cent. Hence, the assumption of chemical equilibrium in MC simulations introduces intrinsic errors of a factor of 2 in chemical abundances, luminosities, and luminosity ratios.

79 ASTRONOMY AND ASTROPHYSICS↗

Laboratory Anion Chemistry: Implications for the DIBs, and a Potential Formation Mechanism for a Known Interstellar Molecule

Due to recent interest in molecular anions as possible interstellar species, we have carried out several laboratory studies of anion chemistry. The reactions of the series C(sub n)(sup -); and C(sub n)H(sup -) with H and H2 were studied to address the viability of such species in the diffuse interstellar medium and to address their ability to be carriers of the diffuse interstellar bands (DIBs). These same molecules were also reacted with N and O to show possible heteroatomic products. C(sub m)N(sup - was a particularly stable product from the reaction of C(sub n)(sup -) + N. C3N(sup -) was further reacted with H to study chemistry that could produce HC3N, a known interstellar species. The reactions were done in a flowing afterglow selected ion flow tube apparatus (FA-SIFT). The anions were generated in an electron impact or cold cathode discharge source and the anion of interest was then selected by a quadrupole mass filter. The selected ion was then reacted with the atomic or molecular species in the flow tube and products were detected by another quadrupole. While the C(sub n)(sup -) species do not appear to be viable DIB carriers, their possible presence could provide a mechanism for the formation of known heteroatomic neutral molecules detected in the interstellar medium (ISM).

Eichelberger, B.↗

Ultraviolet Irradiation of Pyrimidine in Interstellar Ice Analogs: Formation and Photo-Stability of Nucleobases

Astrochemistry laboratory experiments recently showed that molecules of prebiotic interest can potentially form in space, as supported by the detection of amino acids in organic residues formed by the UV photolysis of ices simulating interstellar and cometary environments (H2O, CO, CO2, CH3OH, NH3, etc.). Although the presence of amino acids in the interstellar medium (ISM) is still under debate, experiments and the detection of amino acids in meteorites both support a scenario in which prebiotic molecules could be of extraterrestrial origin, before they are delivered to planets by comets, asteroids, and interplanetary dust particles. Nucleobases, the informational subunits of DNA and RNA, have also been detected in meteorites, although they have not yet been observed in the ISM. Thus, these molecules constitute another family of prebiotic compounds that can possibly form via abiotical processes in astrophysical environments. Nucleobases are nitrogen-bearing cyclic aromatic species with various functional groups attached, which are divided into two classes: pyrimidines (uracil, cytosine, and thymine) and purines (adenine and guanine). In this work, we study how UV irradiation affects pyrimidine mixed in interstellar ice analogs (H2O, NH3, CH3OH). In particular, we show that the UV irradiation of H2O:pyrimidine mixtures leads to the production of oxidized compounds including uracil, and show that both uracil and cytosine are formed upon irradiation of H2O:NH3:pyrimidine mixtures. We also study the photostability of pyrimidine and its photoproducts formed during these experiments.

Nuevo, Michel↗

Gas Phase Spectroscopy of Cold PAH Ions: Contribution to the Interstellar Extinction and the Diffuse Interstellar Bands

Polycyclic Aromatic Hydrocarbon molecules (PAHs) are ubiquitous in the interstellar medium (ISM) and constitute the building blocks of interstellar dust grains. Despite their inferred important role in mediating the energetic and chemical processes in thc ISM, their exact contribution to the interstellar extinction, and in particular to the diffuse interstellar bands (DIBs) remains unclear. The DIBs are spectral absorption features observed in the line of sight of stars that are obscured by diffuse interstellar clouds. More than 200 bands have been reported to date spanning from the near UV to the near IR with bandwidths ranging from 0.4 to 40 Angstroms (Tielens & Snow 1995). The present consensus is that the DIBs arise from free flying, gas-phase, organic molecules and/or ions that are abundant under the typical conditions reigning in the diffuse ISM. PAHs have been proposed as possible carriers (Allamandola et al. 1985; Leger & DHendecourt 1985). The PAH hypothesis is consistent with the cosmic abundance of Carbon and Hydrogen and with the required photostability of the DIB carriers against the strong VUV radiation field in the diffuse interstellar clouds. A significant fraction of PAHs is expected to be ionized in the diffuse ISM.

Biennier, L.↗

The 5-8 Micron Infrared Spectrum of the Galactic Center and the Composition of Interstellar Dust

Interstellar dust is an important component of the interstellar medium which dominates the opacity and, hence, regulates radiative transfer, molecule formation, and thermal balance of the ISM. Much of our knowledge on the composition of interstellar dust results from infrared spect,oscopy. The extinction along the line of sight towards the galactic center is believed to be dominated by dust in the diffuse ISM. Because of the high extinction and high IR flux, IR spectra of galactic center sources have been a prime sampling ground for the characteristics of interstellar dust. We have obtained 5-8 micrometer spectra of the galactic center using the KAO. These spectra show absorption features at 5.5, 5.8, 6.1, and 6.8 micrometers. Together with features in the 3 micrometer region previously observed by us using the IRTF, these features are compared to laboratory spectra of candidate materials. We conclude that the 3.0 and 6.1 micrometer feature are carried by H2O, likely in the form of water of hydration in interstellar silicates. The 3.4, 5.5, 5.8, and 6.8 micrometer features are due to CH2, CH3 and C=O stretching and deformation modes in a hydrocarbon grain component. Comparing derived dust abundances, we conclude that silicates dominate the interstellar dust volume. Hydrocarbon and (small) graphite grains contribute each about 0.1. The remainder of the interstellar dust volume does not show strong IR absorption features and is likely in the form of large graphite, amorphous, carbon, or diamond grains.

Tielens, A. G. G. M.↗

The Exobiological Role of Interstellar Polycyclic Aromatic Hydrocarbons and Ices

Tremendous strides have been made in our understanding of interstellar material over the past twenty years thanks to significant, parallel developments in observational astronomy and laboratory astrophysics. Before this time, the composition of interstellar dust was largely guessed-at, the presence of ices in interstellar clouds ignored, and the notion that large, gas phase, carbon rich molecules might be abundant and widespread throughout the interstellar medium (ISM) considered impossible. Today, the composition of dust in the ISM is reasonably well constrained to micron-sized cold refractory materials comprised of amorphous and crystalline silicates mixed with an amorphous carbonaceous material containing aromatic structural units and short, branched aliphatic chains. Shrouded within the protective confines of cold, opaque molecular clouds--the birthplace of stars and planets--these cold dust particles secrete mantles of mixed molecular ices whose compositions are also well constrained. Finally, amidst the molecular inventory of these ice mantles are likely to be found polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by the standards of interstellar chemistry, the telltale infrared spectral signature of which is now recognized throughout the Universe. In the first part of this talk, we will review the spectroscopic evidence that forms the basis for the currently accepted abundance and ubiquity of PANs in the ISM. We will then look at a few specific examples which illustrate how experimental and theoretical data can be applied to interpret the interstellar spectra and track how the PAN population evolves as it passes from its formation site in the circumstellar outflows of dying stars, through the various phases of the ISM, and into forn~iing planetary systems. Nevertheless, despite the fact that PANs likely represent the single largest molecular reservoir of organic carbon in evolving planetary systems, they are not what would be considered "biogenic" molecules. Although interesting from a chemical and astrophysical standpoint, in the absence of a mechanism by which this population can be dislodged from the precipitous thermodynamic well afforded by their extensive aromatic networks, they are of little Astrobiological significance. Consequently, for the remainder of the talk, we will consider the photochemical evolution of PANS under conditions similar to those found in the ISM and in proto-planetary systems with an eye toward means by which this rich repository of pre-biotic organic "ore" might be converted into materials of greater importance to Astrobiology.

Hudgins, Douglas M.↗

New Infrared Emission Features and Spectral Variations in Ngc 7023

We observed the reflection nebula NGC 7023, with the Short-High module and the long-slit Short-Low and Long-Low modules of the Infrared Spectrograph on the Spitzer Space Telescope. We also present Infrared Array Camera (IRAC) and Multiband Imaging Photometer for Spitzer (MIPS) images of NGC 7023 at 3.6, 4.5, 8.0, and 24 m. We observe the aromatic emission features (AEFs) at 6.2, 7.7, 8.6, 11.3, and 12.7 m, plus a wealth of weaker features. We find new unidentified interstellar emission features at 6.7, 10.1, 15.8, 17.4, and 19.0 m. Possible identifications include aromatic hydrocarbons or nanoparticles of unknown mineralogy. We see variations in relative feature strengths, central wavelengths, and feature widths, in the AEFs and weaker emission features, depending on both distance from the star and nebular position (southeast vs. northwest).

molecules↗

Electronically Excited States of Anistropically Extended Singly-Deprotonated PAH Anions

Polycyclic Aromatic Hydrocarbons (PAHs) play a significant role in the chemistry of the interstellar medium (ISM) as well as in hydrocarbon combustion. These molecules can have high levels of diversity with the inclusion of heteroatoms and the addition or removal of hydrogens to form charged or radical species. There is an abundance of data on the cationic forms of these molecules, but there have been many fewer studies on the anionic species. The present study focuses on the anionic forms of deprotonated PAHs. It has been shown in previous work that PAHs containing nitrogen heteroatoms (PANHs) have the ability to form valence excited states giving anions electronic absorption features. This work analyzes how the isoelectronic pure PAHs behave under similar structural constructions. Singly-deprotonated forms of benzene, naphthalene, anthracene, and teteracene classes are examined. None of the neutral-radicals possess dipole moments large enough to support dipole-bound excited states in their corresponding closed-shell anions. Even though the PANH anion derivatives support valence excited states for three-ringed structures, it is not until four-ringed structures of the pure PAH anion derivatives that valence excited states are exhibited. However, anisotropically-extended PAHs larger than tetracene will likely exhibit valence excited states. The relative energies for the anion isomers are very small for all of the systems in this study.

Theis, Mallory L.↗

The AstroBiology Explorer (ABE) MIDEX Mission Concept: Using Infrared Spectroscopy to Identify Organic Molecules in Space

One of the principal means by which organic compounds are detected and identified in space is by infrared spectroscopy. Past IR studies (telescopic and laboratory) have demonstrated that much of the carbon in the interstellar medium (ISM) is in complex organic species of a variety of types, but the distribution, abundance, and evolutionary relationships of these materials are not well understood. The Astrobiology Explorer (ABE) is a MIDEAST mission concept designed to conduct IR spectroscopic observations to detect and identify these materials to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. Systematic studies include the observation of planetary nebulae and stellar outflows, protostellar objects, Solar System Objects, and galaxies, and multiple lines of sight through dense molecular clouds and the diffuse ISM. ABE will also search for evidence of D enrichment in complex molecules in all these environments. The mission is currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corp. ABE is a cryogenically-cooled 60 cm diameter space telescope equipped with 3 cryogenic cross-dispersed spectrographs that share a single common slit. The 3 spectrometers each measure single spectral octaves (2.5-5, 5-10, 10-20 microns) and together cover the entire 2.5 - 20 micron region simultaneously. The spectrometers use state-of-the-art 1024x1024 pixel detectors, with a single InSb array for the 2.5-5 micron region and two Si:As arrays for the 5-10 and 10-20 micron regions. The spectral resolution is wavelength dependent but is greater than 2000 across the entire spectral range. ABE would operate in a heliocentric, Earth drift-away orbit and is designed to take maximum advantage of this environment for cooling, thermal stability, and mission lifetime. ABE would have a core science mission lasting approximately 1.5 years.

Sandford, Scott A.↗

Infrared Emission From Interstellar PAHs, New Probes of the Interstellar Medium

Tremendous strides have been made in the understanding of interstellar material over the past twenty years thanks to significant, parallel developments in two closely related areas: observational IR astronomy and laboratory astrophysics. Twenty years ago the composition of interstellar dust was largely unknown and the notion of abundant, gas phase, polycyclic aromatic hydrocarbons (PAHs) anywhere in the interstellar medium (ISM) considered impossible. Today the dust composition of the diffuse and dense ISM is reasonably well constrained and the spectroscopic case for interstellar PAHs, impossibly large molecules by early interstellar chemistry standards, is very strong. PAH spectral features are now being used as new probes of the ISM. PAH ionization states reflect the ionization balance of the medium while PAH size and structure reflect the energetic and chemical history of the medium. Aromatic carbon-rich materials ranging in size from PAHs and PAH nanoclusters, to sub-micron and micron-sized dust grains represent an important component of the ISM. These species: (1) dominate the heating and cooling of interstellar clouds via energetic photoelectron ejection and infrared (IR) emission; (2) moderate the ionization balance in photodissociation regions and molecular clouds; (3) moderate the composition of the gas phase and play an important role in determining the chemistry of the ISM; (4) contribute to the interstellar extinction in the near IR, visible, and UV spectral regions; and (5) convert UV, visible, and near-IR radiation to mid- and far-IR radiation in the ISM and, as such, are responsible for the well known, widespread family of mid-IR emission features with major components near 3.3, 6.2, 7.7, 8.6, and 11.3 microns.

Hudgins, D. M.↗

Identifying Organic Molecules in Space: The AstroBiology Explorer (ABE) MIDEX Mission Concept

Infrared spectroscopy in the 2.5-16 micron range is a principle means by which organic compounds are detected and identified in space. Ground-based, airborne, and spaceborne IR spectral studies have already demonstrated that a significant fraction of the carbon in the interstellar medium (ISM) resides in the form of complex organic molecular species. Unfortunately, neither the distribution of these materials nor their genetic and evolutionary relationships with each other or their environments are well understood. The Astrobiology Explorer (ABE) is a MIDEX mission concept currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corporation. ABE will conduct IR spectroscopic observations to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. The core observational program would make fundamental scientific progress in understanding (1) the evolution of ices and organic matter in dense molecular clouds and young forming stellar systems, (2) the chemical evolution of organic molecules in the ISM as they transition from AGB outflows to planetary nebulae to the general diffuse ISM to H II regions and dense clouds, (3) the distribution of organics in the diffuse ISM, (4) the nature of organics in the Solar System (in comets, asteroids, satellites), and (5) the nature and distribution of organics in local galaxies. The technical considerations of achieving these science objectives in a MIDEX-sized mission will be described.

Sandford, Scott A.↗

Detecting and Identifying Organic Molecules in Space: The AstroBiology Explorer (ABE) MIDEX Mission Concept

Infrared spectroscopy in the 2.5-16 microns (4000-625/cm) range is a principle means by which organic compounds are detected and identified in space. Ground-based, airborne, and spaceborne IR spectral studies have already demonstrated that a significant fraction of the carbon in the interstellar medium (ISM) resides in the form of complex organic molecular species. Unfortunately, neither the distribution of these materials nor their genetic and evolutionary relationships with each other or their environments are well understood. The Astrobiology Explorer (ABE) is a MIDEX (Medium-class Explorer) mission concept currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corporation. ABE will conduct IR spectroscopic observations to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. The core observational program would make fundamental scientific progress in understanding (1) the evolution of ices and organic matter in dense molecular clouds and young forming stellar systems, (2) the chemical evolution of organic molecules in the ISM as they transition from AGB outflows to planetary nebulae to the general diffuse ISM to H II regions and dense clouds, (3) the distribution of organics in the diffuse ISM, (4) the nature of organics in the Solar System (in comets, asteroids, satellites), and (5) the nature and distribution of organics in local galaxies. Both the scientific goals of the mission and how they would be achieved will be discussed.

Sandford, Scott A.↗

Detecting and Identifying Organic Molecules in Space - The AstroBiology Explorer (ABE) MIDEX Mission Concept

Infrared spectroscopy in the 2.5-16 micron (4000-625/cm) range is a principle means by which organic compounds are detected and identified in space. Ground-based, airborne, and spaceborne IR spectral studies have already demonstrated that a significant fraction of the carbon in the interstellar medium (ISM) resides in the form of complex organic molecular species. Unfortunately, neither the distribution of these materials nor their genetic and evolutionary relationships with each other or their environments are well understood. The Astrobiology Explorer (ABE) is a MIDEX (Medium-class Explorer) mission concept currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corporation. ABE will conduct IR spectroscopic observations to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. The core observational program would make fundamental scientific progress in understanding (1) the evolution of ices and organic matter in dense molecular clouds and young forming stellar systems, (2) the chemical evolution of organic molecules in the ISM as they transition from AGB outflows to planetary nebulae to the general diffuse ISM to H II regions and dense clouds, (3) the distribution of organics in the diffuse ISM, (4) the nature of organics in the Solar System (in comets, asteroids, satellites), and (5) the nature and distribution of organics in local galaxies. Both the scientific goals of the mission and how they would be achieved will be discussed.

Sandford, Scott A.↗

Radiation Processing of Polycyclic Aromatic Hydrocarbons (PAHs) in Space: ICEE PoC

Small Polycyclic Aromatic Hydrocarbon molecules or PAHs (<30 carbon atoms) have been identified in comets, meteorites, asteroids, and interplanetary dust particles in our Solar System, while PAHs in the Interstellar Medium (ISM) tend to be much larger, usually between 50 to 100 carbon atoms in size. The cause of the size disparity between PAHs found in the ISM and Solar System as well as their influence on Solar System organics is not yet understood. Two chemical evolutionary paths have been proposed to explain the inventory of solar system organics. In one the prebiotic material was formed from the radiation induced modification of large pre-solar carbon-bearing species (e.g. ISM PAHs). The second path suggests that Solar System prebiotic matter is the result of bottom-up synthesis from small reactive molecules after the Solar System was formed. In this second scenario very few ISM PAHs survived the harsh pre-solar radiation as aromatic structures. ICEE PoC (ICEE Proof of Concept) investigated factors impacting the chemical evolution of large PAHs irradiated under conditions similar to the proto-solar nebula. Likewise ICEE PoC will refine the technical parameters of the proposed ICEE (Institute for Carbon Evolution Experiment) laboratory.

Mattioda, Andrew↗

Nucleobases and Prebiotic Molecules in Organic Residues Produced from the Ultraviolet Photo-Irradiation of Pyrimidine in NH3 and H2O+NH3 Ices

Although not yet identified in the interstellar medium (ISM), N-heterocycles including nucleobases the information subunits of DNA and RNA are present in carbonaceous chondrites, which indicates that molecules of biological interest can be formed in non-terrestrial environments via abiotic pathways. Recent laboratory experiments and ab-initio calculations have already shown that the irradiation of pyrimidine in pure H2O ices leads to the formation of a suite of oxidized pyrimidine derivatives, including the nucleobase uracil. In the present work, NH3:pyrimidine and H2O:NH3:pyrimidine ice mixtures with different relative proportions were irradiated with UV photons under astrophysically relevant conditions. Liquid- and gas-chromatography analysis of the resulting organic residues has led to the detection of the nucleobases uracil and cytosine, as well as other species of prebiotic interest such as urea and small amino acids. The presence of these molecules in organic residues formed under abiotic conditions supports scenarios in which extraterrestrial organics that formed in space and were subsequently delivered to telluric planets via comets and meteorites could have contributed to the inventory of molecules that triggered the first biological reactions on their surfaces.

Nuevo, Michel↗

The Rest-frame Submillimeter Spectrum of High-redshift, Dusty, Star-forming Galaxies from the SPT-SZ Survey

We present the average rest-frame spectrum of the final catalog of dusty star-forming galaxies (DSFGs) selected from the South Pole Telescope's SPT-SZ survey and measured with Band 3 of the Atacama Large Millimeter/submillimeter Array. This work builds on the previous average rest-frame spectrum, given in Spilker et al. (2014) for the first 22 sources, and is comprised of a total of 78 sources, normalized by their respective apparent dust masses. The spectrum spans 1.9 < z < 6.9 and covers rest-frame frequencies of 240–800 GHz. Combining this data with low-J CO observations from the Australia Telescope Compact Array, we detect multiple bright line features from 12 CO, [Ci], and H 2 O, as well as fainter molecular transitions from 13 CO, HCN, HCO + , HNC, CN, H 2 O + , and CH. We use these detections, along with limits from other molecules, to characterize the typical properties of the interstellar medium (ISM) for these high-redshift DSFGs. We are able to divide the large sample into subsets in order to explore how the average spectrum changes with various galaxy properties, such as effective dust temperature. We find that systems with hotter dust temperatures exhibit differences in the bright 12 CO emission lines, and contain either warmer and more excited dense gas tracers or larger dense gas reservoirs. These observations will serve as a reference point to studies of the ISM in distant luminous DSFGs (L IR > 10 12 L ⊙ ), and will inform studies of chemical evolution before the peak epoch of star formation at z = 2–3.

79 ASTRONOMY AND ASTROPHYSICS↗