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.     

Detection of a new interstellar molecular ion, H2COH+ (protonated formaldehyde)

A new interstellar molecular ion, H2COH+ (protonated formaldehyde), has been detected toward Sgr B2, Orion KL, W51, and possibly in NGC 7538 and DR21(OH). Six transitions were detected in Sgr B2(M). The 1(1,0)-1(0,1) transition was detected in all sources listed above. Searches were also made toward the cold, dark clouds TMC-1 and L134N, Orion (3N, 1E), and a red giant, IRC + 10216, without success. The excitation temperatures of H2COH+ are calculated to be 60-110 K, and the column densities are on the order of 10(12)-10(14) cm-2 in Sgr B2, Orion KL, and W51. The fractional abundance of H2COH+ is on the order of 10(-11) to 10-(9), and the ratio of H2COH+ to H2CO is in the range 0.001-0.5 in these objects. The values in Orion KL seem to be consistent with the "early time" values of recent model calculations by Lee, Bettens, & Herbst, but they appear to be higher than the model values in Sgr B2 and W51 even if we take the large uncertainties of column densities of H2CO into account. We suggest production routes starting from CH3OH may play an important role in the formation of H2COH+.     

Interstellar cyanomethane

We have made an observational study of the newly identified cyanomethane radical CH2CN and the possibly related species CH3CN with the goals of (1) elucidating the possible role of reactions of the type CnHm(+) + N in astrochemistry, and (2) providing a possible test of Bates's models of dissociative electron recombination. We find a remarkably different abundance ratio CH2CN/CH3CN in TMC-1 and Sgr B2, which we deduce is a result of the large difference in temperature of these objects. Studies of CH2CN and CH3CN in other sources, including two new detections of CH2CN, support this conclusion and are consistent with a monotonic increase in the CH2CN/CH3CN ratio with decreasing temperature over the range 10-120 K. This behavior may be explained by the destruction of CH2CN by reaction with O. If this reaction does not proceed, then CH2CN and CH3CN are concluded to form via different chemical pathways. Thus, they do not provide a test of Bates's conjectures (they do not both form from CH3CNH+). CH2CN is then likely to form via C2H4(+) + N --> CH2CNH+, thus demonstrating the viability of this important reaction in astrochemistry. The T dependence of the CH2CN/CH3CN ratio would then reflect the increasing rate of the C2H4(+) + N reaction with decreasing temperature.     

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.     

Observations of H2S toward OMC-1

Interstellar hydrogen sulfide (H2S) and its isotopic variant (H2(34)S) have been observed toward several positions in OMC-1 via their 1(10)-1(01) transitions near 168 GHz using the FCRAO 14 m telescope. We derive total column densities toward Orion(KL) for the extended ridge, for the plateau, and for the hot core, in addition to values for other positions in OMC-1. The fractional abundance of H2S (approximately 10(-9)) in the quiescent regions of OMC-1 seems to be difficult to explain by currently known ion-molecule reactions. The fractional abundance of H2S relative to H2 is enhanced by a factor of 1000 in the hot core and the plateau relative to the quiescent clouds. This enhancement may be a result of grain surface chemistry and/or of high-temperature gas-phase chemistry. From the nondetection of HDS in its 2(11)-2(12) transition, we estimate the abundance ratio [HDS]/H2S] < or = 0.02 in the hot core.     

Calculations concerning interstellar isomeric abundance ratios for C3H and C3H2

The syntheses of interstellar c-C3H2, H2CCC, c-C3H, and HCCC, where "c" stands for the cyclic isomer, are thought to proceed via dissociative recombination of the precursor ions c-C3H3+ and H2CCCH+, which are themselves produced mainly via the radiative association reaction between C3H+ and H2. We have utilized ab initio methods to study the potential energy surface (PES) for the association of the linear ion C3H+ and H2 to form the isomers c-C3H3+ and H2CCCH+. The overall rate coefficient for radiative association has been calculated as a function of temperature via the phase space method. Our ab initio calculations show that the H2CCCH+ isomer is formed directly without an activation barrier from reactants, and that isomerization between the two isomers can occur readily via a low-energy pathway consisting of two transition states (saddle points on the PES) and one intermediate (local minimum on the PES). Calculations of the equilibrium coefficient for the isomerization H2CCCH+ <-> c-C3H3+ as a function of energy shows that equal abundances of these two ions should be produced as relaxation proceeds, in agreement with experimental measurements at high pressure. Our results confirm the important point that a simple ion-molecule association reaction can produce a cyclic hydrocarbon. If dissociative recombination reactions involving c-C3H3+ and H2CCCH+ maintain the carbon skeletal structure of the ions and produce roughly similar C3H/C3H2 branching ratios, then abundance ratios of unity are produced between the cyclic and noncyclic isomers of C3H and C3H2 via this mechanism. The large abundance ratio of c-C3H2 to H2CCC observed in TMC-1 can then be explained by differential destruction rates.     

Cyanide and isocyanide abundances in the cold, dark cloud TMC-1

We have observed emission from HCN, H13CN, HC15N, HN13C, H15NC, HC3N, CH3CN, and possibly CH3NC, and determined an upper limit for NH2CN, toward the cold, dark cloud TMC-1. The abundance ratio [HNC]/[HCN] = 1.55 +/- 0.16 is at least a factor approximately 4 and approximately 100 greater than that observed toward the giant molecular clouds DR 21(OH) and Orion KL, respectively. In contrast, for the corresponding methylated isomers we obtain [CH3NC]/CH3CN] < or approximately 0.1. We also find [NH2CN]/[CH3CN] < or approximately 0.1 and [HC3N]/[CH3CN] = 30 +/- 10. We find no evidence for anomalous hyperfine ratios for H13CN, indicating that the ratios for HCN (cf. recent work of Walmsley et al.) are the result of self-absorption by cold foreground gas.     

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).     

Interstellar SiO as a tracer of high-temperature chemistry

The J = 2-1 transition of SiO has been searched for toward both hot and cold molecular gas. SiO was not detected toward the dark clouds TMC-1, L134 N, and B335, down to column density upper limits of N < 2-4 x 10(10) cm-2. The species, however, has been observed toward all sources with a kinetic temperature greater than or equal to 30 K, with the largest column densities (N approximately 10(13)-10(17) cm-2) measured in the warmest (TK > or = 100 K) material. The abundance of SiO, relative to HCN, is found to be approximately 0.1-1 in the massive star-forming regions toward Orion and NGC 7538; toward the dark clouds, the upper limits to this ratio is less than 0.0002-0.004. A similar enhancement in the warmer regions is reflected in the SiO/H2 ratio as well. A linear relation was found between the natural log of the SiO concentration and 1/TK, suggesting that the species' formation involves a chemically specific process that contains an activation barrier of approximately 90 K. SiO was also found to be underabundant with respect to SO in cold clouds, with SiO/SO < 1/1000, versus SiO/SO > or =, measured in Orion-KL. The formation of SiO is therefore linked closely to the local gas kinetic temperature, rather than the oxygen abundance, and its synthesis is likely to involve high-temperature gas-phase reactions. The species thus may serve as an unambiguous indicator of high-temperature or "shock" chemistry.     

Astronomical identification of the C3H radical

The C3H radical, a linear carbon chain with a 2 pi electronic ground state, has been identified in the millimeter-wave spectra of two astronomical sources, IRC +10216 and TMC-1, and conclusively confirmed (accompanying Letter) in a laboratory glow discharge. In IRC +10216 four rotational transitions have been observed, three in the lower fine-structure ladder (2 pi 1/2) and one in the upper (2 pi 3/2), each a resolved or partially resolved lambda-doublet. In TMC-1, both lambda components of the lowest lying 3/2 --> 1/2 transition of the 2 pi 1/2 ladder have been observed, each with well-resolved hfs. In IRC +10216 the excitation of C3H is similar to that of SiCC: the rotational temperature Trot within the 2 pi 1/2 ladder is low (8.5 K), owing to rapid radiative decay, while Trot across the ladders is high (approximately 52 K) because interconnecting far-IR radiative transitions are only weakly permitted. The column density of C3H in IRC +10216 averaged over the estimated source diameter of 84" is 2.8 x 10(13) cm-2, an order of magnitude less than that of C2H and C4H. A determination of the spectroscopic constraints of C3H that permitted the entire radio spectrum of this molecule to be calculated to high accuracy has been derived from analysis of the combined astronomical and laboratory data presented in the accompanying Letter.     

An upper limit to the acetylene abundance toward BN in the Orion molecular cloud

We report a search for the acetylene (C2H2) nu 3 infrared vibration-rotation absorption near 3 micrometers toward the Becklin-Neugebauer source in the Orion molecular cloud. The relative abundance of C2H2/CO in the quiescent gas (9 km s-1 component) is less than 3 x 10(-3) (5 sigma).     

First astronomical detection of the cumulene carbon chain molecule H2C6 in TMC-1

The cumulene carbenes are important components of hydrocarbon chemistry in low-mass star-forming cores. Here we report the first astronomical detection of the long-chain cumulene carbene H2C6 in the interstellar cloud TMC-1, from observations of two of its rotational transitions: J(K,K') = 7(1,7) --> 6(1,6) at 18.8 GHz and 8(1,8) --> 7(1,7) at 21.5 GHz, using NASA's Deep Space Network 70 m antenna at Goldstone, California. In addition we also observed the shorter cumulene carbene H2C4 at the same position. The fractional abundance of H2C6 relative to H2 is about 4.7 x 10(-11) and that of H2C4 is about 4.1 x 10(-9). The abundance of H2C6 is in fairly good agreement with gas-phase chemical models for young molecular cloud cores, but the abundance of H2C4 is significantly larger than predicted.     

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.     

Chlorine-bearing molecules in cold and warm interstellar clouds

A new time-dependent model of chlorine chemistry in cold and warm TMC-1 and Orion clouds was constructed using results of recent laboratory and theoretical studies on the reaction of chlorine molecules. The chemistry of chlorine was found to be fairly simple in dense interstellar clouds. Only the species Cl and HCl have a significant fractional abundance. Our results for the HCl molecule are in agreement with those obtained from the observation and from theoretical values of Orion cloud.     

Large-Scale Mapping Observations of the C i (3P1-3P0) and CO (J = 3-2) Lines toward the Orion A Molecular Cloud

Large-scale mapping observations of the 3P1-3P0 fine-structure transition of atomic carbon (C i, 492 GHz) and the J=3-2 transition of CO (346 GHz) toward the Orion A molecular cloud have been carried out with the Mount Fuji submillimeter-wave telescope. The observations cover 9 deg2 and include the Orion Nebula M42 and the L1641 dark cloud complex. The C i emission extends over almost the entire region of the Orion A cloud and is surprisingly similar to that of 13CO (J=1-0). The CO (J=3-2) emission shows a more featureless and extended distribution than C i. The C i/CO (J=3-2) integrated intensity ratio shows a spatial gradient running from the north (0.10) to the south (1.2) of the Orion A cloud, which we interpret as a consequence of the temperature gradient. On the other hand, the C i/13CO (J=1-0) intensity ratio shows no systematic gradient. We have found a good correlation between the C i and 13CO (J=1-0) intensities over the Orion A cloud. This result is discussed on the basis of photodissociation region models.     

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.     

Measurements of the H2(13)CO ortho/para ratio in cold dark molecular clouds.

H2(13)CO has been detected for the first time toward cold dark molecular clouds using the NRAO 12 m telescope. The H2(13)CO ortho/para abundance ratio R for B335, which we report as R approximately 1.7, suggests equilibrium at the local kinetic temperature and appears to be distinctly different from that for both TMC-1 and L134N, where R is close to or higher than the statistical value 3. Since only B335 among the observed positions includes an imbedded IR source, this difference may result from heating of the grain surfaces, providing the energy necessary for desorption of formaldehyde formed on the grains.     

A search for HCCN in molecular clouds

We have conducted a deep search for HCCN towards the dark cloud TMC-l and several GMC's via its N(J) = 1(2)-->0(1) transition. HCCN was not detected in any of these sources. Towards TMC-l, assuming optically thin emission, the total column density upper limit is NHCCN < or = 2 x 10(12) cm-2, which corresponds to a fractional abundance upper limit with respect to molecular hydrogen of fHCCN < or = 2 x 10(-10). We find the abundance ratio of HCN:HCCN:HCCCN in TMC-l to be l : <0.01 : 0.3, which suggests that carbon-chain growth by the addition of single carbon atoms may not be efficient under dark cloud conditions. The HCCN abundance limit also places constraints on the branching ratio for the products of the dissociative electron recombination H3C2N+ + e.     

Detection of a new interstellar molecule, H2CN

We have detected a new interstellar molecule, H2CN (methylene amidogen), in the cold, dark molecular cloud TMC-l. The column density of H2CN is estimated to be approximately 1.5 x 10(11) cm-2 by assuming an excitation temperature of 5 K. This column density corresponds to a fractional abundance relative to H2 of approximately 1.5 x 10(-11). This value is more than three orders of magnitude less than the abundance of the related molecule HCN in TMC-1. We also report a tentative detection of H2CN in Sgr B2(N). The formation mechanism of H2CN is discussed. Our detection of the H2CN molecule may suggest the existence of a new series of carbon-chain molecules, CH2CnN (n = 0, 1, 2,...).     

Variations in the HCN/HNC abundance ratio in the Orion molecular cloud

We have used observations of the rare isotopes of HCN and HNC to determine the relative abundance of these two chemical isomers along the central ridge of the Orion molecular cloud. The abundance ratio [HCN]/[HNC] decreases by more than an order of magnitude from the relatively warm plateau and hot core sources toward the KL nebula to the colder, more quiescent clouds to the north and south. Even in the cooler regions, however, the ratio is an order of magnitude larger than that found in previous investigations of cold dark clouds. We determine the kinetic temperature in the regions we have studied from new observations of methylacetylene (CH3CCH), together with other recent estimates of the gas temperature near KL. The results suggest that the warmer portions of the cloud are dominated by different chemical pathways than those in the general interstellar cloud material.