Martin A. Cordiner

The UMIST database for astrochemistry 2012

We present the fifth release of the UMIST Database for Astrochemistry (UDfA). The new reaction network contains 6173 gas-phase reactions, involving 467 species, 47 of which are new to this release. We have updated rate coefficients across all reaction types. We have included 1171 new anion reactions and updated and reviewed all photorates. In addition to the usual reaction network, we also now include, for download, state-specific deuterated rate coefficients, deuterium exchange reactions and a list of surface binding energies for many neutral species. Where possible, we have referenced the original source of all new and existing data. We have tested the main reaction network using a dark cloud model and a carbon-rich circumstellar envelope model. We present and briefly discuss the results of these models.

The Large Magellanic Cloud: diffuse interstellar bands, atomic lines and the local environmental conditions

The Large Magellanic Cloud (LMC) offers a unique laboratory to study the diffuse interstellar bands (DIBs) under conditions that are profoundly different from those in the Galaxy. DIB carrier abundances depend on several environmental factors, in particular the local UV radiation field. In this paper we present measurements of twelve DIBs in five lines of sight to early-type stars in the LMC, including the 30 Doradus region. From the high resolution spectra obtained with VLT/UVES we also derive environmental parameters that characterise the local interstellar medium (ISM) in the probed LMC clouds. These include the column density components (including total column density) for the atomic resonance lines of Na I, Ca II, Ti II, K I. In addition, we derive the H I column density from 21 cm line profiles, the total-to-selective visual extinction RV and the gas-to-dust ratio N(H I)/A_V. Furthermore, from atomic line ratios we derive the ionisation balance and relative UV field strength in these environments. We discuss the properties of the LMC ISM in the context of DIB carrier formation. The behaviour of DIBs in the LMC is compared to that of DIBs in different local environmental conditions in the Milky Way. A key result is that in most cases the diffuse band strengths are weak (up to factor 5) with respect to Galactic lines of sight of comparable reddening, EB-V. In the line of sight towards Sk -69 223 the 5780 and 5797 �DIBs are very similar in strength and profile to those observed towards HD 144217 , which is typical of an environment exposed to a strong

Interstellar gas, dust and diffuse bands in the SMC

Aims. In order to gain new insight into the unidentified identity of the diffuse interstellar band (DIB) carriers, this paper describes research into possible links between the shape of the interstellar extinction curve (including the 2175 A bump and far-UV rise), the presence or absence of DIBs, and physical and chemical conditions of the diffuse interstellar medium (gas and dust) in the Small Magellanic Cloud (SMC). Methods. We searched for DIB absorption features in VLT/UVES spectra of early-type stars in the SMC whose reddened lines-ofsight probe the diffuse interstellar medium of the SMC. Apparent column density profiles of interstellar atomic species (Na i ,K i ,C aii and Ti ii) are constructed to provide information on the distribution and conditions of the interstellar gas. Results. The characteristics of eight DIBs detected toward the SMC wing target AzV 456 are studied and upper limits are derived for the DIB equivalent widths toward the SMC stars AzV 398, AzV 214, AzV 18, AzV 65 and Sk 191. The amount of reddening is derived for these SMC sightlines, and, using RV and the H i column density, converted into a gas-to-dust ratio. From the atomic column density ratios we infer an indication of the strength of the interstellar radiation field, the titanium depletion level and a relative measure of turbulence/quiescence. The presence or absence of DIBs appears to be related to the shape of the extinction curve, in particular with respect to the presence or absence of the 2175 A feature. Our measurements indicate that the DIB characteristics depend on the local physical conditions and chemical composition of the interstellar medium of the SMC, which apparently determine the rate of formation (and/or) destruction of the DIB carriers. The UV radiation field (via photoionisation and photo-destruction) and the metallicity (i.e. carbon abundance) are important factors in determining diffuse band strengths which can differ greatly both between and within galaxies.

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-butadiene 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.

Multi-epoch high-resolution spectroscopy of SN 2011fe - Linking the progenitor to its environment

Context. The nearby Type Ia SN 2011fe has provided an unprecedented opportunity to derive some of the properties of the progenitor system, which is one of the key open problems in the supernova (SN) field. Aims. This study attempts to establish a link between the reasonably well known nature of the progenitor and its surrounding environment. This is done with the aim of enabling the identification of similar systems in the vast majority of the cases, when distance and epoch of discovery do not allow a direct approach. Methods. To study the circumstellar environment of SN 2011fe we have obtained high-resolution spectroscopy of SN 2011fe on 12 epochs, from 8 to 86 days after the estimated date of explosion, targeting in particular at the time evolution of Caii and Nai. Results. Three main absorption systems are identified from Caii and Nai, one associated to the Milky Way, one probably arising within a high-velocity cloud, and one most likely associated to the halo of M101. The Galactic and host galaxy reddening, deduced from the integrated equivalent widths (EW) of the Nai lines are EB V=0.011 0.002 and EB V=0.014 0.002 mag, respectively. The host galaxy absorption is dominated by a component detected at the same velocity measured from the 21-cm Hi line at the projected SN position ( 180 km s 1 ). During the 3 months covered by our observations, its EW changed by 15.6 6.5 mA. This small variation is shown to be compatible with the geometric e ects produced by the rapid SN photosphere expansion coupled to the patchy fractal structure of the ISM. The observed behavior is fully consistent with ISM properties similar to those derived for our own Galaxy, with evidences for structures on scales .100 AU. Conclusions. SN 2011fe appears to be surrounded by a ”clean” environment. The lack of blue-shifted, time-variant absorption features is fully consistent with the progenitor being a binary system with a main-sequence, or even another degenerate star.

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 15N. 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 15N 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 15N enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, 15N 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 15N and D in dense cloud cores. We also show that while the nitriles, HCN and HNC, contain the greatest 15N enrichment, this is not expected to correlate with extreme D enrichment. These calculations therefore support the view that solar system 15N 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.

THE ABUNDANCE OF C3H2 AND OTHER SMALL HYDROCARBONS IN THE DIFFUSE INTERSTELLAR MEDIUM

Hydrocarbons are ubiquitous in the interstellar medium, observed in diverse environments ranging from diffuse to molecular dark clouds and strong photon-dominated regions near HII regions. Recently, two broad diffuse interstellar bands (DIBs) at 4881{\AA} and 5450{\AA} were attributed to the linear version of propynylidene l-C3H2, a species whose more stable cyclic conformer c-C3H2 has been widely observed in the diffuse interstellar medium at radio wavelengths. This attribution has already been criticized on the basis of indirect plausibility arguments because the required column densities are quite large, N(l-C3H2)/EB-V = 4 \times 1014 cm-2 mag-1. Here we present new measurements of N(l-C3H2) based on simultaneous 18-21 GHz VLA absorption profiles of cyclic and linear C3H2 taken along sightlines toward extragalactic radiocontinuum background sources with foreground Galactic reddening EB-V = 0.1 - 1.6 mag. We find that N(l-C3H2)/N(c-C3H2) ? 1/15 - 1/40 and N(l-C3H2)/EB-V ? 2 \pm 1 \times 1011 cm-2 mag-1, so that the column densities of l-C3H2 needed to explain the diffuse interstellar bands are some three orders of magnitude higher than what is observed. We also find N(C4H)/EB-V < 1.3 \times 1013 cm-2 mag-1 and N(C4H-)/EB-V < 1 \times 1011 cm-2 mag-1 (3?). Using available data for CH and C2H we compare the abundances of small hydrocarbons in diffuse and dark clouds as a guide to their ability to contribute as DIB carriers over a wide range of conditions in the interstellar medium.

A SURVEY OF DIFFUSE INTERSTELLAR BANDS IN THE ANDROMEDA GALAXY: OPTICAL SPECTROSCOPY OF M31 OB STARS

We present the largest sample to date of intermediate-resolution blue-to-red optical spectra of B-type supergiants in M31 and undertake the first survey of diffuse interstellar bands (DIBs) in this galaxy. Spectral classifications, radial velocities, and interstellar reddenings are presented for 34 stars in three regions of M31. Based on a subset of these stars with foreground-corrected reddening E M 31 B?V ? 0.05, the strengths of the M31 DIBs are analyzed with respect to the amount of dust, ultraviolet radiation field strength, and polycyclic aromatic hydrocarbon emission flux. Radial velocities and equivalent widths are given for the ?5780 and ?6283 DIBs toward 11 stars. Equivalent widths are also presented for the following DIBs detected in three sightlines in M31: ??4428, 5705, 5780, 5797, 6203, 6269, 6283, 6379, 6613, 6660, and 6993. All of these M31 DIB carriers reside in clouds at radial velocities matching those of interstellar Na I and/or H I. The relationships between DIB equivalent widths and reddening (E M 31 B?V ) are consistent with those observed in the local interstellar medium (ISM) of the Milky Way (MW). Many of the observed sightlines show DIB strengths (per unit reddening) which lie at the upper end of the range of Galactic values. DIB strengths per unit reddening are found (with 68% confidence) to correlate with the interstellar UV radiation field strength. The strongest DIBs are observed where the interstellar UV flux is lowest. The mean Spitzer 8/24 ?m emission ratio in our three fields is slightly lower than that measured in the MW, but we identify no correlation between this ratio and the DIB strengths in M31. Interstellar oxygen abundances derived from the spectra of three M31 H II regions in one of the fields indicate that the average metallicity of the ISM in that region is 12 + log [O/H] = 8.54 ? 0.18, which is approximately equal to the value in the solar neighborhood.

DISCOVERY OF INTERSTELLAR ANIONS IN CEPHEUS AND AURIGA

We report the detection of microwave emission lines from the hydrocarbon anion C6H– and its parent neutral C6H in the star-forming region L1251A (in Cepheus), and the pre-stellar core L1512 (in Auriga). The carbon-chain-bearing species C4H, HC3N, HC5N, HC7N, and C3S are also detected in large abundances. The observations of L1251A constitute the first detections of anions and long-chain polyynes and cyanopolyynes (with more than five carbon atoms) in the Cepheus Flare star-forming region, and the first detection of anions in the vicinity of a protostar outside of the Taurus molecular cloud complex, indicating a possible wider importance for anions in the chemistry of star formation. Rotational excitation temperatures have been derived from the HC3N hyperfine structure lines and are found to be 6.2 K for L1251A and 8.7 K for L1512. The anion-to-neutral ratios are 3.6% and 4.1%, respectively, which are within the range of values previously observed in the interstellar medium, and suggest a relative uniformity in the processes governing anion abundances in different dense interstellar clouds. This research contributes toward the growing body of evidence that carbon chain anions are relatively abundant in interstellar clouds throughout the Galaxy, but especially in the regions of relatively high density and high depletion surrounding pre-stellar cores and young, embedded protostars.

ETHYL CYANIDE ON TITAN: SPECTROSCOPIC DETECTION AND MAPPING USING ALMA

We report the first spectroscopic detection of ethyl cyanide (C2H5CN) in Titan’s atmosphere, obtained using spectrally and spatially resolved observations of multiple emission lines with the Atacama Large Millimeter/ submillimeter Array (ALMA). The presence of C2H5CN in Titan’s ionosphere was previously inferred from Cassini ion mass spectrometry measurements of C2H5CNH + . Here we report the detection of 27 rotational lines from C2H5CN (in 19 separate emission features detected at s >3 confidence) in the frequency range 222–241 GHz. Simultaneous detections of multiple emission lines from HC3N, CH3CN, and CH3CCH were also obtained. In contrast to HC3N, CH3CN, and CH3CCH, which peak in Titan’s northern (spring) hemisphere, the emission from C2H5CN is found to be concentrated in the southern (autumn) hemisphere, suggesting a distinctly different chemistry for this species, consistent with a relatively short chemical lifetime for C2H5CN. Radiative transfer models show that C2H5CN is most concentrated at altitudes200 km, suggesting production predominantly in the stratosphere and above. Vertical column densities are found to be in the range (1–5) ×1 0 14 cm �2 .