Searches for new interstellar molecules, including a tentative detection of aziridine and a possible detection of propenal.

Rotational spectroscopy at millimeter wavelengths is a powerful means of investigating the chemistry of dense interstellar clouds. These regions can exhibit an interesting complement of gas phase molecules, including relatively complex organics. Here we report the tentative first astronomical detection of aziridine (ethylenimine), the possible detection of propenal (acrolein), and upper limits on the abundances of cyclopropenone, furan, hydroxyethanal (glycolaldehyde), thiohydroxylamine (NH2SH), and ethenol (vinyl alcohol) in various interstellar clouds.

Detection of nitrogen sulfide in Comet Hale-Bopp.

We report the first detection of the nitrogen sulfide (NS) radical in a comet. The abundance relative to water is at least a few hundredths of a percent for Comet Hale-Bopp.

Chemistry of the organic-rich hot core G327.3-0.6.

We present gas-phase abundances of species found in the organic-rich hot core G327.3-0.6. The data were taken with the Swedish-ESO Submillimetre Telescope (SEST). The 1-3 mm spectrum of this source is dominated by emission features of nitrile species and saturated organics, with abundances greater than those found in many other hot cores, including Sgr B2 and OMC-1. Population diagram analysis indicates that many species (CH3CN, C2H3CN, C2H5CN, CH3OH, etc.) have hot components that originate in a compact (~2") region. Gas-phase chemical models cannot reproduce the high abundances of these molecules found in hot cores, and we suggest that they originate from processing and evaporation of icy grain mantle material. In addition, we report the first detection of vibrationally excited ethyl cyanide and the first detection of methyl mercaptan (CH3SH) outside the Galactic center.

The formaldehyde ortho/para ratio as a probe of dark cloud chemistry and evolution.

We present measurements of the H2CO ortho/para ratio toward four star-forming cores, L723, L1228, L1527, and L43, and one quiescent core, L1498. Combining these data with earlier results by Minh et al., three quiescent cores are found to have ortho/para ratios near 3, the ratio of statistical weights expected for gas-phase formation processes. In contrast, ortho/para ratios are 1.5-2.1 in five star-forming cores, suggesting thermalization at a kinetic temperature of 10 K. We attribute modification of the ortho/para ratio in the latter cores to formation and/or equilibration of H2CO on grains with sub-sequent release back into the gas phase due to the increased energy inputs from the forming star and outflow. We see accompanying enhancements in the H2CO abundance relative to H, to support this idea. The results suggest that the formaldehyde ortho/para ratio can differentiate between quiescent cores and those in which low-mass star formation has occurred.

The composition of interstellar molecular clouds.

We consider four-aspects of interstellar chemistry for comparison with comets: molecular abundances in general, relative abundances of isomers (specifically, HCN and HNC), ortho/para ratios for molecules, and isotopic fractionation, particularly for the ratio hydrogen/deuterium. Since the environment in which the solar system formed is not well constrained, we consider both isolated dark clouds where low mass stars may form and the "hot cores" that are the sites of high mass star formation. Attention is concentrated on the gas phase, since the grains are considered elsewhere in this volume.

Chemistry in cometary comae.

Significant gas-phase chemistry occurs in the comae of bright comets, as is demonstrated here for the case of Comet Hale-Bopp. The abundance ratio of the two isomers, hydrogen cyanide and hydrogen isocyanide, is shown to vary with heliocentric distance in a way that is consistent with production of HNC by ion-molecule chemistry initiated by the photoionization of water. Likewise, the first maps of emission from HCO+ show an abundance and an extended distribution that are consistent with the same chemical model.

Extraterrestrial organic matter: a review.

We review the nature of the widespread organic material present in the Milky Way Galaxy and in the Solar System. Attention is given to the links between these environments and between primitive Solar System objects and the early Earth, indicating the preservation of organic material as an interstellar cloud collapsed to form the Solar System and as the Earth accreted such material from asteroids, comets and interplanetary dust particles. In the interstellar medium of the Milky Way Galaxy more than 100 molecular species, the bulk of them organic, have been securely identified, primarily through spectroscopy at the highest radio frequencies. There is considerable evidence for significantly heavier organic molecules, particularly polycyclic aromatics, although precise identification of individual species has not yet been obtained. The so-called diffuse interstellar bands are probably important in this context. The low temperature kinetics in interstellar clouds leads to very large isotopic fractionation, particularly for hydrogen, and this signature is present in organic components preserved in carbonaceous chondritic meteorites. Outer belt asteroids are the probable parent bodies of the carbonaceous chondrites, which may contain as much as 5% organic material, including a rich variety of amino acids, purines, pyrimidines, and other species of potential prebiotic interest. Richer in volatiles and hence less thermally processed are the comets, whose organic matter is abundant and poorly characterized. Cometary volatiles, observed after sublimation into the coma, include many species also present in the interstellar medium. There is evidence that most of the Earth's volatiles may have been supplied by a 'late' bombardment of comets and carbonaceous meteorites, scattered into the inner Solar System following the formation of the giant planets. How much in the way of intact organic molecules of potential prebiotic interest survived delivery to the Earth has become an increasingly debated topic over the last several years. The principal source for such intact organics was probably accretion of interplanetary dust particles of cometary origin.

Chemical processing in the coma as the source of cometary HNC.

The discovery of hydrogen isocyanide (HNC) in comet Hyakutake with an abundance (relative to hydrogen cyanide, HCN) similar to that seen in dense interstellar clouds raised the possibility that these molecules might be surviving interstellar material. The preservation of material from the Sun's parent molecular cloud would provide important constraints on the processes that took place in the protostellar nebula. But another possibility is that HNC is produced by photochemical processes in the coma, which means that its abundance could not be used as a direct constraint on conditions in the early Solar System. Here we show that the HNC/HCN ratio determined for comet Hale-Bopp varied with heliocentric distance in a way that matches the predictions of models of gas-phase chemical production of HNC in the coma, but cannot be explained if the HNC molecules were coming from the comet's nucleus. We conclude that HNC forms mainly by chemical reactions in the coma, and that such reactions need to be considered when attempting to deduce the composition of the nucleus from observations of the coma.

Abundances of ethylene oxide and acetaldehyde in hot molecular cloud cores.

We have searched for millimetre-wave line emission from ethylene oxide (c-C2H4O) and its structural isomer acetaldehyde (CH3CHO) in 11 molecular clouds using SEST. Ethylene oxide and acetaldehyde were detected through multiple lines in the hot cores NGC 6334F, G327.3-0.6, G31.41+0.31, and G34.3+0.2. Acetaldehyde was also detected towards G10.47+0.03, G322.2+0.6, and Orion 3'N, and one ethylene oxide line was tentatively detected in G10.47+0.03. Column densities and rotational excitation temperatures were derived using a procedure which fits the observed line intensifies by finding the minimum chi 2-value. The resulting rotational excitation temperatures of ethylene oxide and acetaldehyde are in the range 16-38 K, indicating that these species are excited in the outer, cooler parts of the hot cores or that the excitation is significantly subthermal. For an assumed source size of 20", the deduced column densities are (0.6-1)x10(14) cm-2 for ethylene oxide and (2-5)x10(14) cm-2 for acetaldehyde. The fractional abundances with respect to H2 are X[c-C2H4O]=(2-6)xl0(-10), and X[CH3CHO]=(0.8-3)x10(-9). The ratio X[CH3CHO]/X[c-C2H4O] varies between 2.6 (NGC 6334F) and 8.5 (G327.3-0.6). We also detected and analysed multiple transitions of CH3OH, CH3OCH3, C2H5OH, and HCOOH. The chemical, and possibly evolutionary, states of NGC 6334F, G327.3-0.6, G31.41+0.31, and G34.3+0.2 seem to be very similar.

Are clouds collapsing at the 2' north position of Sagittarius B2?

The 3 mm lines of HCO2+ and HNCO have been observed toward Sgr B2. Besides the well-known "principal cloud" and an extended envelope, we find another gas cloud 2' north of Sgr B2(M). This 2' north (2' N) cloud which may be located behind the principal cloud, has a total mass of approximately 10(5) Msolar and a diameter of approximately 7 pc. HCO2+ and HNCO exist mainly at 2' north, and their column densities are about 2.2 x 10(14) and 2.3 x 10(15) cm-2, respectively. The fractional abundances of these species relative to molecular hydrogen appear to be enhanced by at least a factor of 10 compared to the principal cloud. We have also identified redshifted and blueshifted high-velocity components which move toward the 2' N position with projected velocities of +/- 30 km s-1. These components are located symmetrically around 2' N, along the Galactic plane, and have diameters of about 4-5 pc and masses of approximately 1 x 10(4) Msolar. The flow energies are large enough to initiate new star formation in the 2' N region on the free-fall timescale of 10(5) yr. This large-scale collapsing motion may cause a strong shock in the 2' N cloud and result in the enhancement of HCO2+ and HNCO.

HCO+ imaging of comet Hale-Bopp (C/1995 O1).

The HCO+ J = 1-0 rotational transition at 89.189 GHz has been mapped in comet Hale-Bopp (C/1995 O1) over a total of 38 individual days spanning the period 1997 March 10-June 20 with the Five College Radio Astronomy Observatory 14 m antenna. HCO+ is detectable over an extended region of the comet, with the peak emission commonly located 50,000-100,000 km in the antisolar direction. Maps made throughout the apparition show significant variability in the structure of the HCO+ coma, sometimes on timescales of several hours. The HCO+ brightness is usually depressed at the nucleus position, and on some occasions, the emission is spread into a ring around the position of the nucleus. Individual spectra within the maps display broad (approximately 4 km s-1) lines redshifted by 1-2 km s-1 or more from the nominal velocity of the nucleus, with the redshift typically increasing in the antisolar direction. The spectra and maps may be generally explained by models in which the ions are accelerated tailward at a rate on the order of 10 cm s-2, provided that HCO+ is destroyed within 50,000-100,000 km of the nucleus.

Chemical and physical gradients along the OMC-1 ridge.

We present a survey of the distribution of 20 chemical and isotopic molecular species along the central ridge of the Orion molecular cloud from 6' north to 6' south of BN-KL observed with the QUARRY focal plane array on the FCRAO 14 m telescope, which provides an angular resolution of approximately 50" in the 3 mm wavelength region. We use standard tools of multivariate analysis for a systematic investigation of the similarities and differences among the maps of integrated intensities of the 32 lines observed. The maps fall in three broad classes: first, those strongly peaked toward BN-KL; second, those having rather flat distributions along the ridge; and third, those with a clear north-south gradient or contrast. We identify six positions or regions where we calculate relative abundances. Line velocities and line widths indicate that the optically thin lines generally trace the same volume of dense gas, except in the molecular bar, where C18O, C34S, H13CO+, CN, C2H, SO, and C3H2 have velocities characteristic of the bar itself, whereas the emission from other detected species is dominated by the background cloud. The strongest abundance variations in our data are the well-known enhancements seen in HCN, CH3OH, HC3N, and SO toward BN-KL and, less strongly, toward the Orion-South outflow 1'.3S. The principal result of this study is that along the extended quiescent ridge the chemical abundances, within factors of 3-4, exhibit an impressive degree of uniformity. The northern part of the ridge has a chemistry closest to that found in quiescent dense clouds. While temperature and density are similar around the northern radical-ion peak near 3'.5N and in the southern core near 4'.2S, some abundances, in particular, those of the ions HCO+ and N2H+, are significantly lower toward 4'.2S. The areas near 4.'2S and the molecular bar itself around (1'.7E, 2'.4S) stand out with peculiar and similar properties probably caused by stronger UV fields penetrating deeper into the clumpy molecular gas. This leads to higher electron abundances and thereby reduced abundances of the ions, as well as a lack of complex molecules.

A survey of the chemical properties of the M17 and Cepheus A cloud cores.

We present the results of a systematic survey of the chemical properties of two giant molecular cloud (GMC) cores in M17 and Cepheus A. In all, we have mapped the emission from 32 molecular transitions of 13 molecules and seven isotopic variants over a 4' x 5' region in each core. Each map includes known sites of massive star formation, as well as the more extended quiescent material. In M17 most molecules have emission peaks away from the H II region/molecular cloud interface, while two species, HC3N and CH3C2H, deviate from this structure with sharp maxima closer to this interface. In Cepheus A the core is influenced by a compact high-velocity molecular outflow and a more extended low-velocity flow. The molecular emission distributions in this source are generally quite similar, with most molecules peaking near the center of the core to the east of the compact H II region HW 2. A few molecules, SO, CH3OH, H13CN, and C18O, have more extended emission. Only two molecules, CO and HCO+, appear to trace the high- and low-velocity outflows; all other species are tracing the quiescent core. We have used the results of previous studies of the density and temperature of the dense gas in the same cloud cores to derive accurate abundances relative to CO for several positions in each core. The principal result is that the chemical composition of all the cores we have surveyed (which include OMC-1 as well as M17 and Cepheus A) show remarkable similarity, both within a given core and among the cores. This suggests that the chemical processes are similar in quiescent GMC core material. In M17 the lack of variation of molecular abundances is remarkable because the radiation field and the gas temperature are known to vary appreciably throughout the surveyed region, suggesting that the bulk of the emission arises from gas that is well shielded from radiation.

Hydrogenation of interstellar molecules: a survey for methylenimine (CH2NH).

Methylenimine (CH2NH) has been convincingly detected for the first time outside the Galactic center as part of a study of the hydrogenation of interstellar molecules. We have observed transitions from energy levels up to about 100 K above the ground state in the giant molecular clouds W51, Orion KL and G34.3 + 0.15. In addition, CH2NH was found at the " radical-ion peak" on the quiescent ridge of material in the Orion molecular cloud. The abundance ratio CH2NH/HCN at the radical-ion peak agrees with the predictions of recent gas-phase chemical models. This ratio is an order of magnitude higher in the warmer cloud cores, suggesting additional production pathways for CH2NH, probably on interstellar grains.

Nitrogen sulfide in giant molecular clouds.

We report a survey for nitrogen sulfide (NS) toward regions of massive star formation. NS was observed by means of its 2 pi 1/2, J = 3/2 --> 1/2, J = 5/2 --> 3/2, and J = 7/2 --> 5/2 transitions at 69, 115, and 161 GHz, respectively, and was detected toward 12 of 14 giant molecular clouds (GMCs) observed. Analysis of the hyperfine component relative line strengths suggests that NS emission is optically thin toward these sources, with the possible exception of Sgr B2(M). The fractional abundance of NS relative to molecular hydrogen is best defined for the Orion molecular cloud, where it is typically (1-4) x 10(-10), which is about an order of magnitude larger than found by some recent gas-phase chemistry models developed for quiescent clouds. Toward OMC-1, the NS integrated intensity is strongly peaked toward KL, but also extends all along the Orion ridge, resembling the distribution of SO and CH3OH. We have identified a spectral feature seen toward several sources as the ortho-NKK = 4(04) --> 3(13) J = 3 --> 2, fine-structure component of methylene (CH2; cf. Hollis, Jewell, & Lovas). We also report the first detection of the SO+ 2 pi 1/2, J = 3/2 --> 1/2, parity-e transition toward W51(MS) and L134N.

The HNC/HCN ratio in comets.

The abundance ratio of the isomers HCN and HNC has been investigated in comet Hale-Bopp (C/1995 O1) through observations of the J = 4-3 rotational transitions of both species for heliocentric distances 0.93 < r < 3 AU, both pre- and post-perihelion. After correcting for the optical depth of the stronger HCN line, we find that the column density ratio of HNC/HCN in our telescope beam increases significantly as the comet approaches the Sun. We compare this behavior to that predicted from an ion-molecule chemical model and conclude that the HNC is produced in significant measure by chemical processes in the coma; i.e., for comet Hale-Bopp, HNC is not a parent molecule sublimating from the nucleus.

Collisional quenching of OH radio emission from comet Hale-Bopp.

Observations of comets in the 18-cm OH transitions offer a means to probe gas production, kinematics, and OH excitation in comets. We present initial results of OH observations of comet Hale-Bopp obtained with the NRAO 43 m antenna located in Greenbank, WV. Maps of the emission provide strong constraints on the amount of quenching of the inversion of the OH ground state A-doublet in the coma. Analysis of the total radio OH flux and maps of its radial brightness distribution indicate a quenched region on the order of approximately 500,000 km during March and April 1997. This large value is generally consistent with previous observations of radio OH quenching in lower production rate comets when the high production rate of comet Hale-Bopp is considered.

HCO+ in the coma of comet Hale-Bopp.

Maps of comet C/1995 O1 (Hale-Bopp) in the millimeter-wave emission of the ion HCO+ revealed a local minimum near the nucleus position, with a maximum about 100,000 km in the antisolar direction. These observed features of the HCO+ emission require a low abundance of HCO+ due to enhanced destruction in the inner coma of the comet, within a region of low electron temperature (Te). To set constraints on the formation of HCO+ in the coma, as well as the location and magnitude of the transition to higher Te, the data are compared with the results of ion-molecule chemistry models.

A study of the physics and chemistry of TMC-1.

We present a comprehensive study of the physical and chemical conditions along the TMC-1 ridge. Temperatures were estimated from observations of CH3CCH, NH3, and CO. Densities were obtained from a multitransition study of HC3N. The values of the density and temperature allow column densities for 13 molecular species to be estimated from statistical equilibrium calculations, using observations of rarer isotopomers where possible, to minimize opacity effects. The most striking abundance variations relative to HCO+ along the ridge were seen for HC3N, CH3CCH, and SO, while smaller variations were seen in CS, C2H, and HCN. On the other hand, the NH3, HNC, and N2H+ abundances relative to HCO+ were determined to be constant, indicating that the so-called NH3 peak in TMC-1 is probably a peak in the ammonia column density rather than a relative abundance peak. In contrast, the well-studied cyanopolyyne peak is most likely due to an enhancement in the abundance of long-chain carbon species. Comparisons of the derived abundances to the results of time-dependent chemical models show good overall agreement for chemical timescales around 10(5) yr. We find that the observed abundance gradients can be explained either by a small variation in the chemical timescale from 1.2 x 10(5) to 1.8 x 10(5) yr or by a factor of 2 change in the density along the ridge. Alternatively, a variation in the C/O ratio from 0.4 to 0.5 along the ridge produces an abundance gradient similar to that observed.

Detection of interstellar ethylene oxide (c-C2H4O).

We report the identification of 10 transitions that support the detection of the small cyclic molecule ethylene oxide (c-C2H4O) in Sgr B2N. Although one of these transitions is severely blended, so that an accurate intensity and line width could not be determined, and two other lines are only marginally detected, we have done Gaussian fits to the remaining seven lines and have performed a rotation diagram analysis. Our results indicate a rotation temperature T(rot) = 18 K and a molecular column density N(c-C2H4O) = 3.3 x 10(14) cm-2, corresponding to a fractional abundance relative to molecular hydrogen of order 6 x 10(-11). This is a factor of more than 200 higher than the abundance for this molecule suggested by the "new standard" chemistry model of Lee, Bettens, & Herbst. This result suggests that grain chemistry might play an effective role in the production of c-C2H4O. No transitions of this molecule were detected in either Sgr B2M or Sgr B2NW.