Nitrogen sulfide in quiescent dark clouds

We report the first detection of interstellar nitrogen sulfide (NS) in cold dark clouds. Several components of the 2 pi 1/2, J = 3/2 --> 1/2 and J = 5/2 --> 3/2 transitions were observed in TMC-1 and L134N. The inferred column density for TMC-1 is NNS approximately 8 x 10(12)cm-2 toward the NH3 peak in that cloud, and in L134N is NNS approximately 3 x 10(12)cm-2 toward the position of peak NH3 emission. These values correspond to fractional abundances relative to molecular hydrogen of fNS approximately 8 x 10(-10) for TMC-1, and fNS approximately 6 x 10(-10) for L134N. The NS emission is extended along the TMC-1 ridge and is also extended in L134N. The measured abundances are significantly higher than those predicted by some recent gas phase ion-molecule models.     

The detection of acetaldehyde in cold dust clouds

Observations of the 1(01) --> 0(00) rotational transitions of A and E state acetaldehyde are reported. The transitions were detected, for the first time in interstellar space, in the cold dust clouds TMC-1 and L134N, and in Sgr B2. This is also the first time acetaldehyde has been found in a dust cloud and is the most complex oxygen-bearing molecule yet known in this environment. We find a column density of 6 x 10(12) cm-2 in TMC-1, comparable to many other species detected there, and an approximately equal column density in L134N. In the direction of Sgr B2, the CH3CHO profile appears to consist of broad emission features from the hot molecular cloud core, together with absorption features resulting from intervening colder material. We also report the possible detection of HC9N toward IRC +10 degrees 216 through its J = 33 --> 32 transition. Implications for cold dust cloud chemistry and excitation are discussed.     

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,...).     

Detection of interstellar hydrogen sulfide in cold, dark clouds

We have detected interstellar hydrogen sulfide (H2S) toward the cold, dark clouds L134N and TMC 1. We derive total column densities of approximately 2.6 x 10(13) cm-2 and approximately 7.0 x 10(12) cm-2 at the SO peak of L134N and at the NH3 peak of TMC 1, respectively. Since the expected gas phase reactions leading to the formation of H2S are thought to be endothermic, grain surface reactions may play a major role in the synthesis of this species in cold, dark clouds. If the carbon abundance is high and grain surface reactions are the dominant formation route, H2CS would be expected to form instead of H2S, and the abundances of H2CS have been observed to be high where those of H2S are low in L134N and TMC 1.     

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.     

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+.     

The detection of interstellar methylcyanoacetylene

A new interstellar molecule, methylcyanoacetylene (CH3C3N), has been detected in the molecular cloud TMC-1. The J = 8 --> 7, J = 7 --> 6, J = 6 --> 5, and J = 5 --> 4 transitions have been observed. For the first three of these, both the K = 0 and K = 1 components are present, while for J = 5 --> 4, only the K = 0 line has been detected. The observed frequencies were calculated by assuming a value of radial velocity VLSR = 5.8 km s-1 for TMC-1, typical of other molecules in the cloud. All observed frequencies are within 10 kHz of the calculated frequencies, which are based on the 1982 laboratory constants of Moises et al., so the identification is secure. The lines are broadened by hyperfine splitting, and the J = 5 --> 4, K = 0 transition shows incipient resolution into three hyperfine components. The rotational temperature determined for these observations is quite low, with 2.7 K < or = Trot < or = 4 K. the total column density is approximately 5 x 10(12) cm-2.     

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.     

Interferometric observations for oxygen-containing organic molecules toward Orion-KL

High spatial resolution observations (approximately 5") were made for the 3 mm transitions of methanol (CH3OH), methyl formate (HCOOCH3), and dimethyl ether [(CH3)2O] toward Orion-KL using the Nobeyama Millimeter Array. The 15(3)-14(4) A- CH3OH emission appears to be elongated along the line connecting IRc2 and "the southern condensation (SC)", which may suggest a relation between methanol and the outflow from IRc2. The HCOOCH3 (7(1,6)-6(1,5)) and (CH3)2O (15(2,13)-15(1,14)) emissions appear to be well concentrated toward SC with an angular size of approximately 6".5 (at the 2 sigma level). There also exists another oxygen-rich condensation to the west of IRc2 (angular size approximately 4".5) having column densities of HCOOCH3 and (CH3)2O comparable to those of SC. We derive the total column densities 6.8 x 10(16) cm-2, 1.4 x 10(16) cm-2 and 2.7 x 10(16) cm-2 for CH3OH, HCOOCH3, and (CH3)2O, respectively, at the core of SC.     

Measurements in N2-CH4(C2H2) discharges of reaction rates and thermochemical constants for Titan atmosphere study

The kinetic reactions in N2-xCH4(C2H2) gas discharges with x less than 1% have been studied by emission spectroscopy in the afterglow of D.C. discharges and by mass spectroscopy from radiolysis ionization using alpha particles. The pressure range is from several Torr to 100 Torr. At the end of N2 D.C. discharges at room temperature, for a residence time of about 10(-2) s, the dominant active species are the N atoms with density of 10(14)-10(15) cm-3 for N2 density of about 10(17) cm-3 (3 Torr), the N2(X,V) vibrational molecules with for example [N2(X,V = 10)] approximately 10(14) cm-3 and the electronic metastable molecules N2(A 3 sigma u +) with a density of 10(12) cm-3. In such conditions, the following kinetic reactions have been studied: N2(A) + N2(A) --> N2(C,B,V') + N2(X), N2(A) + N2(X,V>5) --> N2(X) + N2(B,V') in pure N2 post-discharges and N2(A) + CH4 --> products, C + N + M2 --> CN(B,V') + M2, N2(X,V>4) + CN --> N2(X) + CN(B,A,V'), in N2-1% CH4 post-discharges. The clustering reactions of N2-(1-5%)CH4(C2H2) gas mixtures after radiolysis ionization have been studied for the H2CN+ nN2 ions and the equilibrium constants have been determined in the temperature range T = 140-300 K.     

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.     

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.     

SiS in Orion-KL: evidence for "outflow" chemistry

SiS has been conclusively detected toward Orion-KL via its J = 6-5 and J = 5-4 rotational transitions at 91 and 109 GHz. Line profiles indicate that the species is present at an LSR velocity of 7.5 km s-1 with a half-width at zero power of 36 km s-1. Such characteristics associate SiS with the moderate velocity outflow (V approximately 18 km s-1) centered on IRc2 and observed in thermal SiO, the NH3 "plateau," and OH, H2O, and SiO masers. The column density estimated for SiS in this region is Ntot = 4 x 10(15) cm-2, corresponding to a fractional abundance of f approximately 4 x 10(-9). Such an abundance implies an SiO/SiS ratio of approximately 60 in the outflow material, remarkably close to the cosmic O/S ratio of approximately 40 and contrasting with the SiO/SiS value of > approximately 10(3) predicted by ion-molecule models. This difference is probably a result of the high temperatures and densities present in the outflow, which favor thermal equilibrium abundances similar to those observed in the circumstellar shells of late-type stars rather than "ion-molecule"-type concentrations. In addition to SiS, some twenty new unidentified lines near 91 and 109 GHz were detected toward KL, as well as transitions arising from HC5N, HC13CCN, HCC13CN, O13CS, and, possibly, CH3CH2OH, CH3CHO, and CH3OD.     

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.     

Observations of interstellar HOCO+: abundance enhancements toward the galactic center

A survey of the 4(04)-3(03) and 1(01)-0(00) transitions of HOCO+ has been made toward several molecular clouds. The HOCO+ molecule was not observed in any sources except Sgr B2 and Sgr A. The 5(05)-4(04) and 4(14)-3(13) transitions were also detected toward Sgr B2. The results indicate that gas phase CO2 is not a major carbon reservoir in typical molecular clouds. In Sgr B2, the HOCO+ antenna temperature exhibits a peak approximately 2' north of the Sgr B2 central position (Sgr B2[M]) and the 4(04)-3(03) line emission is extended over a approximately 10' x 10' region. The column density of HOCO+ at the northern peak in Sgr B2 is approximately 3 x 10(14) cm-2, and the fractional abundance relative to H2 > or = 3 x 10(-10), which is about 2 orders of magnitude greater than recent predictions of quiescent cloud ion-molecule chemistry.     

Carbon Dioxide in Star-forming Regions

Observations with the Short Wavelength Spectrometer on board the Infrared Space Observatory have led to the first detection of the methyl radical CH(3) in the interstellar medium. The nu(2) Q-branch at 16.5 μm and the R(0) line at 16.0 μm have been unambiguously detected toward the Galactic center Sagittarius A*. The analysis of the measured bands gives a column density of &parl0;8.0+/-2.4&parr0;x1014 cm(-2) and an excitation temperature of 17+/-2 K. Gaseous CO at a similarly low excitation temperature and C(2)H(2) are detected for the same line of sight. Using constraints on the H(2) column density obtained from C(18)O and visual extinction, the inferred CH(3) abundance is &parl0;1.3+2.2-0.7&parr0;x10-8. The chemically related CH(4) molecule is not detected, but the pure rotational lines of CH are seen with the Long Wavelength Spectrometer. The absolute abundances and the CH(3)/CH(4) and CH(3)/CH ratios are inconsistent with published pure gas-phase models of dense clouds. The data require a mix of diffuse and translucent clouds with different densities and extinctions, and/or the development of translucent models in which gas-grain chemistry, freeze-out, and reactions of H with polycyclic aromatic hydrocarbons and solid aliphatic material are included.     

Infrared spectroscopy of Triton and Pluto ice analogs: the case for saturated hydrocarbons

The infrared transmission spectra and photochemical behavior of various organic compounds isolated in solid N2 ices, appropriate for applications to Triton and Pluto, are presented. It is shown that excess absorption in the surface spectra of Triton and Pluto, i.e., absorption not explained by present models incorporating molecules already identified on these bodies (N2, CH4, CO, and CO2), that starts near 4450 cm-1 (2.25 micrometers) and extends to lower frequencies, may be due to alkanes (C(n)H2n+2) and related molecules frozen in the nitrogen. Branched and linear alkanes may be responsible. Experiments in which the photochemistry of N2:CH4 and N(2):CH4:CO ices was explored demonstrate that the surface ices of Triton and Pluto may contain a wide variety of additional species containing H, C, O, and N. Of these, the reactive molecule diazomethane, CH2N2, is particularly important since it may be largely responsible for the synthesis of larger alkanes from CH4 and other small alkanes. Diazomethane would also be expected to drive chemical reactions involving organics in the surface ices of Triton and Pluto toward saturation, i.e., to reduce multiple CC bonds. The positions and intrinsic strengths (A values) of many of the infrared absorption bands of N2 matrix-isolated molecules of relevance to Triton and Pluto have also been determined. These can be used to aid in their search and to place constraints on their abundances. For example, using these A values the abundance ratios CH4/N2 approximately 1.3 x 10(-3), C2H4/N2 < or = 9.5 x 10(-7) and H2CO/N2 < or = 7.8 x 10(-7) are deduced for Triton and CH4/N2 approximately 3.1 x 10(-3), C2H4/N2 < or = 4.1 x 10(-6), and H2CO/N2 < or = 5.2 x 10(-6) deduced for Pluto. The small amounts of C2H4 and H2CO in the surface ices of these bodies are in disagreement with the large abundances expected from many theoretical models.     

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.     

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).     

The high-latitude cloud MBM 7. I. H I and CO observations

The high-latitude cloud (HLC) MBM 7 has been observed in the 21 cm H I line and the 12CO(1-0) and 13CO(1-0) lines with similar spatial resolutions. The data reveal a total mass approximately 30 M solar for MBM 7 and a complex morphology. The cloud consists of a cold dense core of 5 M solar surrounded by atomic and molecular gas with about 25 M solar, which is embedded in hotter and more diffuse H I gas. We derive a total column density N(H I + 2H2) of 1 x 10(21) cm-2 toward the center and 1 x 10(20) cm-3 toward the envelope of MBM 7. The CO line indicates the existence of dense cores [n(H2) > or = 2000 cm-3] of size (FWHM) approximately 0.5 pc. The morphology suggests shock compression from the southwest direction, which can form molecular cores along the direction perpendicular to the H I distribution. The H I cloud extends to the northeast, and the velocity gradient appears to be about 2.8 km s-1 pc-1 in this direction, which indicates a systematic outward motion which will disrupt the cloud in approximately 10(6) yr. The observed large line widths of approximately 2 km s-1 for CO suggest that turbulent motions exist in the cloud, and hydrodynamical turbulence may dominate the line broadening. Considering the energy and pressure of MBM 7, the dense cores appear not to be bound by gravity, and the whole cloud including the dense cores seem to be expanding. The distance to HLCs suggest that they belong to the galactic plane, since the scale height of the cloud is < or approximately equal to 100 pc. Compared to the more familiar dense dark clouds, HLCs may differ only in their small mass and low density, with their proximity reducing the filling factor and enhancing the contrast of the core and envelope structure.