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 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.

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.

Deuterium in comet C/1995 O1 (Hale-Bopp): detection of DCN.

Deuterated hydrogen cyanide (DCN) was detected in a comet, C/1995 O1 (Hale-Bopp), with the use of the James Clerk Maxwell Telescope on Mauna Kea, Hawaii. The inferred deuterium/hydrogen (D/H) ratio in hydrogen cyanide (HCN) is (D/H)HCN = (2.3 +/- 0.4) x 10(-3). This ratio is higher than the D/H ratio found in cometary water and supports the interstellar origin of cometary ices. The observed values of D/H in water and HCN imply a kinetic temperature >/=30 +/- 10 K in the fragment of interstellar cloud that formed the solar system.

A determination of the HDO/H2O ratio in comet C/1995 O1 (Hale-Bopp).

Deuterated water (HDO) was detected in comet C/1995 O1 (Hale-Bopp) with the use of the James Clerk Maxwell Telescope on Mauna Kea, Hawaii. The inferred D/H ratio in Hale-Bopp's water is (3.3 +/- 0.8) x 10(-4). This result is consistent with in situ measurements of comet P/Halley and the value found in C/1996 B2 (Hyakutake). This D/H ratio, higher than that in terrestrial water and more than 10 times the value for protosolar H2, implies that comets cannot be the only source for the oceans on Earth.

Measurements of 12C/13C, 14N/15N, and 32S/34S ratios in comet Hale-Bopp (C/1995 O1).

The 12C/13C, 14N/15N, and 32S/34S isotope ratios in comet Hale-Bopp (C/1995 O1) were determined through observations taken with the James Clerk Maxwell Telescope. Measurements of rare isotopes in HCN and CS revealed isotope ratios of H12CN/H13CN = 111 +/- 12, HC14N/HC15N = 323 +/- 46, and C32S/C34S = 27 +/- 3. Within the measurement uncertainties, the isotopic ratios are consistent with solar system values. The cometary volatiles thus have an origin in the solar system and show no evidence for an interstellar component.

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.

Spectroscopic evidence for interstellar ices in comet Hyakutake.

Volatile compounds in comets are the most pristine materials surviving from the time of formation of the Solar System, and thus potentially provide information about conditions that prevailed in the primitive solar nebula. Moreover, comets may have supplied a substantial fraction of the volatiles on the terrestrial planets, perhaps including organic compounds that played a role in the origin of life on Earth. Here we report the detection of hydrogen isocyanide (HNC) in comet Hyakutake. The abundance of HNC relative to hydrogen cyanide (HCN) is very similar to that observed in quiescent interstellar molecular clouds, and quite different from the equilibrium ratio expected in the outermost solar nebula, where comets are thought to form. Such a departure from equilibrium has long been considered a hallmark of gas-phase chemical processing in the interstellar medium, suggesting that interstellar gases have been incorporated into the comet's nucleus, perhaps as ices frozen onto interstellar grains. If this interpretation is correct, our results should provide constraints on the temperature of the solar nebula, and the subsequent chemical processes that occurred in the region where comets formed.

Detection of formic acid in the cold, dark cloud L134N.

We report the first detection of formic acid (HCOOH) in a cold, dark interstellar cloud (L134N). The observed abundance of 3x10(-10) relative to H2 is between one and two orders of magnitude lower than that calculated by published ion molecule models of dark cloud chemistry, but is quite consistent with recent model revisions based on new reaction rates. Formic acid was not detected in the archetypical dark cloud TMC-1, and was tentatively detected in the region of massive star formation, W51.

Observations of some oxygen-containing and sulfur-containing organic molecules in cold dark clouds.

Observations of nine oxygen- and sulfur-containing organic molecules have been made toward the cold dark clouds TMC-1 and L134N. We have confirmed the presence of para-ketene (H2C2O) in TMC-1, have for the first time observed ortho-ketene, and find a total ketene column density approximately 1 x 10(13) cm-2. Thioformaldehyde (H2CS) is easily detectable in both TMC-1 and L134N, with a column density about 5 times larger in the former source (approximately 3 x 10(13) cm-2). The fractional abundance of ketene is comparable to the predictions of ion-molecule chemistry, while that of thioformaldehyde in TMC-1 is one to two orders of magnitude greater than that expected from such models at steady state. Interstellar sulfur chemistry thus continues to be poorly understood. We set upper limits for the column densities of formic acid (HCOOH), vinyl alcohol (CH2CHOH), methyl formate (HCO2CH3), formamide (NH2CHO), methyl mercaptan (CH3SH), isothiocyanic acid (HNCS), and thioketene (H2C2S) in both sources.

A survey of cyclopropenylidene (C3H2) in galactic sources.

We report the results of an initial survey in a variety of Galactic sources for cyclopropenylidene (C3H2), the first interstellar hydrocarbon ring molecule. C3H2 is found to be very widespread throughout the Galaxy. This, together with its large dipole moment and many observable transitions, makes cyclopropenylidene a promising probe for physical conditions in the interstellar medium. The ortho 1(10)-1(01) transition at 18 GHz is detected in a variety of environments, including giant molecular clouds, diffuse clouds, cold dark clouds, the spiral arm clouds in the direction of distant continuum sources, and the envelope of the carbon star IRC + 10216. The 2(20)-2(11) para line at 21.6 GHz was surveyed in many sources having strong 1(10)-1(01) emission, and, when detected, it was always seen in absorption. A more limited survey of the ortho 2(12)-1(01) transition at 85.3 GHz has been conducted. In addition, the 2(11)-2(02) line of the para species at 46.8 GHz was detected in the dark clouds TMC-1 and L134N. Maps have been made of the clouds TMC-1, L134N, W51, and Orion, confirming that the C3H2 emission is extended in these objects. The data obtained thus far suggest that C3H2 is one of the more abundant organic constituents of the dense interstellar medium.

A new interstellar polyatomic molecule: detection of propynal in the cold cloud TMC-1.

We report the detection of the acetylene derivative propynal (HC triple bond CCHO) in the cold cloud TMC-1, with an abundance that is very close to that for the related species tricarbon monoxide (C3O). Propadienone, an isomer of propynal with the formula H2C=C=C=O, was not detected and is hence less abundant than either C3O or HC2CHO.

Identification of the interstellar cyanomethyl radical (CH2CN) in the molecular clouds TMC-1 and Sagittarius B2.

We report the astronomical identification of the cyanomethyl radical, CH2CN, the heaviest nonlinear molecular radical to be identified in interstellar clouds. The complex fine and hyperfine structures of the lowest rotational transitions at about 20.12 and 40.24 GHz are resolved in TMC-1, where the abundance appears to be about 5 x 10(-9) relative to that of H2. This is significantly greater than the observed abundance of CH3CN (methyl cyanide) in TMC-1. In Sgr B2 the hyperfine structure is blended in the higher frequency transitions at 40, 80, and 100 GHz, although the spin-rotation doubling is clearly evident. Preliminary searches in other sources indicate that the distribution of CH2CN is similar to that for such carbon chain species as HC3N or C4H.

A study of C3HD in cold interstellar clouds.

We have detected the 1(10)-1(01) transition of C3HD at 19.418 GHz at twelve positions in cold, dark clouds and resolved the D hyperfine components in two sources (L1498 and TMC-1C) well enough to derive values for the D quadrupole coupling constants. Simultaneous observations of C3H2 in each source yield relative integrated line intensities in the range 0.10-0.18, from which we derive relative [C3HD]/[C3H2] abundances in the range 0.05-0.15. These are among the highest deuteration ratios yet observed. Within the limits of the observational and modeling uncertainties it is possible to explain the derived [C3HD]/[C3H2] ratios by ion-molecule chemistry if [e-] approximately 3 x 10(-7).

Newly detected molecules in dense interstellar clouds.

The last year or so has seen the identification of several new interstellar molecules, including C2S, C3S, C5H, C6H, and (probably) HC2CHO in the cold, dark cloud TMC-1; and the discovery of the first interstellar phosphorous-containing molecule, PN, in the Orion "plateau" source. Further interesting results include the observations of 13C3H2 and C3HD, and the first detection of HCOOH (formic acid) in a cold cloud.

Deuterium hyperfine structure in interstellar C3HD.

The deuterium nuclear quadrupole hyperfine structure of the transition 1(10)-1(01) of the ring molecule cyclopropenylidene-d1 (C3HD) has been observed in emission from interstellar molecular clouds. The narrowest linewidths (approximately 7 kHz) so far observed are in the cloud L1498. The derived D coupling constants Xzz = 186.9(1.4) kHz, eta=0.063(18) agree well with correlations based on other molecules.

Observations of OCS and a search for OC3S in the interstellar medium.

Observations of OCS and a search for OC3S are reported, with particular reference to cold dust clouds. OCS has been detected for the first time in dark clouds with a mean fractional abundance relative to hydrogen of approximately 3 x 10(-9); this is approximately 4 times greater than that observed for giant molecular clouds. This results is discussed in the context of molecule formation mechanisms. Observations of the J = 1 --> 0 transition of OCS indicate that this transition is amplifying the background continuum radiation in the direction of Sgr B2.

Detections of 13C-substituted C3H2 in astronomical sources.

We report observations of the 2(12)-1(01) rotational transition of the 13C isotopic species of cyclopropenylidene (C3H2) toward TMC-1, Sgr B2, and IRC +10216 using the laboratory rest frequencies which have recently become available. Our detections allow estimates to be made of the fractional abundance of the unsubstituted similar species in these sources. The fractional abundance relative to H2, f(C3H2), is 1-2 x 10(-8) in TMC-1, and this is similar to the abundance of HCN, one of the more abundant organic molecules in the interstellar medium. In IRC +10216 f(C3H2) is one order of magnitude greater than in TMC-1. The 12C species in Sgr B2 shows a self-absorbed profile and the relative abundance of C3H2 estimated to be about an order of magnitude less than in TMC-1.

The C3H2 2(20)-2(11) transition: absorption in cold dark clouds.

The first observations of the 2(20)-2(11) transition of cyclopropenylidene (C3H2) at 21.6 GHz are described. In all cases where it has been detected, the line appears in absorption, showing that this transition is "refrigerated" (i.e., Tex < 2.7 K) in cold dust clouds. These results are compared with those for the 1(10)-1(01) transition of C3H2, and the consequences for the excitation of C3H2 qualitatively discussed.

New interstellar masers in nonmetastable ammonia.

We report the astronomical detections of several ammonia inversion transitions involving nonmetastable levels with energies as high s 1090 K above the ground state. The (J, K) = (9, 6) inversion transition shows maser-like emission in the directions of W51, NGC 7538, W49, and DR 21(OH). The NH3 (6, 3) line exhibits similar characteristics in W51 but is seen in absorption in NGC 7538. These are the first definite detections of ammonia masers in space. The intensities and narrow line widths (0.5-1.5 km s-1) for the emission features are in contrast to the previously detected broad, weak, nonmetastable lines attributed to thermal emission in these sources. Temporal variability appears to be evident in the (9, 6) emission in W49 over a 4 month period. The highly excited (J, K) = (9, 6) and (6, 3) ammonia lines are found in regions containing compact H II regions and strong infrared sources with associated H2O and OH masers; i.e., in regions of active star formation.