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+.     

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.     

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.     

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.     

The hydrocarbon ring C3H2 is ubiquitous in the Galaxy

We report the discovery of a strong microwave (lambda 1.6 cm) spectral line, the carrier of which is common and widespread throughout the Galaxy. A survey of a large number of sources shows that the line appears in emission in cold dust clouds, in absorption in the direction of the Galactic center, and exhibits complex profiles toward H II regions. Toward Cas A and distant H II regions, intervening "spiral arm" clouds produce absorption. For almost all cases, the absorption features show a striking 1 : 1 radial velocity correspondence with those seen, e.g., in H2CO spectra of the same objects. The data indicate that the line arises between low-lying energy states of rather polar molecule. Recent work by Thaddeus, Vrtilek, and Gottlieb, reported in 1985 incorporating the present data, shows that the line in question is the 1(10)-1(01) transition of the small hydrocarbon ring C3H2.     

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.     

Mass spectrometric study of three-body ion-molecule clustering reactions of CpHq+ ions with N2 or CH4 in N2-CH4 mixtures

Thermochemical data for several ion-molecule clustering of hydrocarbon ions with N2 or CH4 were obtained from clustering equilibria studies in gas mixtures irradiated by alpha-particles. High-pressure mass spectrometry was used to determine the enthalpy and entropy changes of clustering (delta H0 and delta S0, respectively) for the reactions X+(N2)n-1 + 2N2 <==> X(+)(N2)n + N2 with X = CH5, n = 1-2; X = C2H5, n = 1-4; and X = C3H7, n = 1. For X = CH5, the values (delta H0; delta S0) are found to be (-6.8 kcal mol-1; -19.7 cal mol-1 K-1) for n = 1, and (-5.3 kcal mol-1; -15.9 cal mol-1 K-1) for n = 2. For X = C2H5, (delta H0; delta S0) = (-6.9 kcal mol-1; -18.2 cal mol-1 K-1), for n = 1, and (-4.6 kcal mol-1; -20.8 cal mol-1 K-1) for n = 2. From the equilibrium measurements at 129 K, estimates of the thermochemical values could be obtained for n = 3-4. The results obtained for the free energy, delta G0, were -1.4 kcal mol-1 for n = 3, and -1.1 kcal mol-1 for n = 4. For X = C3H7 we found delta G0 = -0.7 kcal mol-1 at 213 K. The association reactions X+ + 2CH4 <==> X+(CH4) + CH4 with X = CH5, C2H5, C2H7, and C3H7 were also studied, resulting in free energy values at 206 K of -3.1, -1.9, -0.5 and -1.3 kcal mol-1, respectively. The results for CH5, C2H5 and C3H7 are compared with previously reported measurements.     

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).     

Cyanide Chemistry in Comet Hale-Bopp (C/1995 O1)

Observations of comet Hale-Bopp (C/1995 O1) have been carried out near perihelion (1997 March) at millimeter wavelengths using the NRAO 12 m telescope. The J=1-->0, 2-->1, and 3-->2 lines of HCN at 88, 177, and 265 GHz were measured in the comet as well as the J=3-->2 lines of H13CN, HC15N, and HNC. The N=2-->1 transition of CN near 226 GHz was also detected, and an upper limit was obtained for the J=2-->1 line of HCNH+. From the measurements, column densities and production rates have been estimated. A column density ratio of [HCN]/[HNC] = 7+/-1 was observed near perihelion, while it was found that [HCN]/[HCNH+] greater, similar 1. The production rates at perihelion for HCN and CN were estimated to be Q(HCN) approximately 1x1028 s-1 and Q(CN) approximately 2.6x1027 s-1, respectively, resulting in a ratio of [HCN]/[CN] approximately 3. Consequently, HCN is sufficiently abundant to be the parent molecule of CN in Hale-Bopp, and HCNH+ could be a source of HNC. Finally, carbon and nitrogen isotope ratios of 12C/13C = 109+/-22 and 14N/15N = 330+/-98 were obtained from HCN measurements, in agreement with previous values obtained from J=4-->3 data. Such ratios suggest that comet Hale-Bopp formed coevally with the solar system.     

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.     

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.     

The infrared spectra of nitriles and related compounds frozen in Ar and H2O

We present the 2320-2050 cm-1 (4.31-4.88 micrometers) infrared spectra of 16 solid-state nitriles, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C triple bond N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile (phenylcyanide), 9-anthracenecarbonitrile, dimethylcyanamide, isopropylnitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyruvonitrile, dicyandiamide, cyanamide, n-butylisocyanide, methylisocyanoacetate, diisopropylcarbodiimide, and hydrogen cyanide. The C triple bond N stretching bands of the majority of nitriles fall in the 2300-2200 cm-1 (4.35-4.55 micrometers) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contrast, the isonitriles and a few exceptional nitriles and related species produce bands at lower frequencies spanning the 2200-2080 cm-1 (4.55-4.81 micrometers) range. These features also have similar positions in both Ar and H2O matrices, and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C triple bond N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165 cm-1 (4.62 micrometers) "XCN" interstellar feature and the 4550 cm-1 (2.2 micrometers) feature of various objects in the solar system are discussed.     

The infrared emission bands. II. A spatial and spectral study of the Orion Bar

We have studied the spectral and spatial distribution across the Orion Bar of the 3-14 micrometers emission, including hydrogen Brackett alpha and 12.8 micrometers [Ne II] emission lines and several "dust" emission features. The data indicate that the "dust" consists of three components; (1) "classical" dust with a temperature of approximately 60 K accounting for emission longward of 20 micrometers, (2) amorphous carbon particles or polycyclic aromatic hydrocarbon (PAH) clusters (approximately 400 C atoms) which produce broad emission features in the 6-9 and 11-13 micrometers bands, and (3) free PAHs which emit in sharper bands (most strongly at 3.3, 6.2, 7.7, 8.6, and 11.3 micrometers). The 3.3 and 11.3 micrometers features, which are due to C-H modes, are well correlated spatially, while the 7.7 micrometers band, due to C=C modes, has a different distribution than the 3.3 and 11.3 micrometers bands. We conclude that the sharp emission bands arise in the photodissociation transition region between the H II region and the molecular cloud and are not present in the H II region. The broad continuum feature extending from 11-13 micrometers is strong in both regions. Previous broad-band observations of the 10 and 20 micrometers flux distributions, which show that the 10 micrometers radiation extends farther into the neutral gas to the south than the 20 micrometers radiation, suggest that some of the 10 micrometers flux is supplied via a nonthermal mechanism, such as fluorescence.     

SME observations of O2 (1 delta g) nightglow: an assessment of the chemical production mechanisms

Solar Mesosphere Explorer (SME) observations of the 3 a.m. 1.27 micrometers nightglow at 45 N latitude, averaged over the period 10-31 July 1984, are reported. From the deduced volume emission rates, we derive the O2(a1 delta g) night-time production rates for the 80-100 km altitude range. Utilizing the mean SME-acquired 3 p.m. ozone profile for the same latitude and time period and an updated photochemical model, we determine night-time O, O3, H, OH, HO2, and H2O2 profiles. These are used in calculating the rates of reactions which are sufficiently exothermic to produce O2(1 delta) or excited states of OH or HO2, which could transfer their energy to O2 to form O2(1 delta). Of these reactions, most have rates that are quite small compared with the observed night-time O2(1 delta) production rate. For several others, laboratory experiments have found O2(1 delta) yields which are insufficient for simulating the observed O2(1 delta). Using yields of O2(1 delta) based on published laboratory and observational studies, we find that the sum of two reaction sequences can approximate the SME measurements: (1) O+O+M and (2) H+O3 followed by OH*+O2.     

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.     

NOBLE GASES IN THE BELLS (C2) AND SHARPS (H3) CHONDRITES

Bells and Sharps have some mineralogical and chemical peculiarities that make their classification uncertain. For Bells, the⁴⁰ Ar content at 890 × 10^?8 cm³ STP/g is greater than the highest C1 chondrite value (Ivuna; 640), but close to the mean value for C2's (880). The²¹ Ne-exposure age of 0.38 ± 0.07 Ma is very short, and coincides with the distinctive cluster of five C2's (0.17 to 0.76 Ma). Very likely Bells belongs to the same cluster, in which case it comes from the C2 parent body. Hence the C2 parent body seems to contain transitional C1-C2 material, like Bells, within a few km of the region of C2 chondrites proper. Thus the radiogenic and especially the cosmogenic gases link Bells to the C2 group. For Sharps, the elemental concentrations of primordial Ar, Kr and Xe (127, 0.76 and 0.59, all 10^?8 cc/g) are ～ 3 x higher than for any other H3 chondrite. While Sharps is classified as 3.4 based on five indicators of metamorphism, the very high concentration of remaining two parameters of the Sears et al. (1980) scheme — C and primordial³⁶ Ar — (together with the high concentration of the volatile trace elements Bi, In and Tl) implies a classification of 3.0 for its volatile element content. The²¹ Ne-exposure age is 25.5 ± 2.5 Ma, placing Sharps in the second largest peak of the H-chondrite distribution. The nominal K-Ar and U, Th-He ages are 4.6 ± 0.2 and 4.2 ± 1.5 Ga, suggesting that Sharps has remained at low temperatures since its beginnings.     

H2 Diagnostics of Magnetic Molecular Shocks in Bipolar Outflows

The shock waves associated with molecular outflows may be of continuous (C) type or jump (J) type, depending on conditions in the preshock gas, notably the magnetic field strength and the degree of ionisation. Intermediate situations also exist, in which a J-discontinuity terminates or is embedded in a C-type flow. We show that proper allowance for the departure of the chemistry from equilibrium (particularly the dissociation/reformation of H₂) and for the inertia of charged dust grains, is crucial for an accurate treatment of the C to J transition. We illustrate the use of H₂ population diagrams and H₂ line profiles, in conjunction with our detailed shock model, to constrain conditions in shocks propagating in molecular outflows. We show that H₂ pure rotational lines yield evidence for C-type precursors in bipolar outflows from young stars, with transverse magnetic field strengths B (μG) ? 1–10 × $\sqrt {n_{H/{\text{cm}}^{ - 3} } } $ similar to those inferred from Zeeman splitting and from the dispersion of dust polarization vectors in dense clouds.     

Observations of CH4, C2H6, and C2H2 in the stratosphere of Jupiter

We have performed high-resolution spectral observations at mid-infrared wavelengths of CH4 (8.14 micrometers), C2H6 (12.16 micrometers), and C2H2 (13.45 micrometers) on Jupiter. These emission features probe the stratosphere of the planet and provide information on the carbon-based photochemical processes taking place in that region of the atmosphere. The observations were performed using our cryogenic echelle spectrometer CELESTE, in conjunction with the McMath-Pierce 1.5-m solar telescope between November 1994 and February 1995. We used the methane observations to derive the temperature profile of the jovian atmosphere in the 1-10 mbar region of the stratosphere. This profile was then used in conjunction with height-dependent mixing ratios of each hydrocarbon to determine global abundances for ethane and acetylene. The resulting mixing ratios are 3.9(+1.9)(-1.3) x 10(-6) for C2H6 (5 mbar pressure level), and 2.3 +/- 0.5 x 10(-8) for C2H2 (8 mbar pressure level), where the quoted uncertainties are derived from model variations in the temperature profile which match the methane observation uncertainties.     

Physical properties of (2) Pallas

Ground-based high angular-resolution images of asteroid (2) Pallas at near-infrared wavelengths have been used to determine its physical properties (shape, dimensions, spatial orientation and albedo distribution).We acquired and analyzed adaptive optics (AO) J/H/K-band observations from Keck II and the Very Large Telescope taken during four Pallas oppositions between 2003 and 2007, with spatial resolution spanning 32-88 km (image scales 13-20 km/pixel). We improve our determination of the size, shape, and pole by a novel method that combines our AO data with 51 visual light-curves spanning 34 years of observations as well as archived occultation data.The shape model of Pallas derived here reproduces well both the projected shape of Pallas on the sky (average deviation of edge profile of 0.4 pixel) and light-curve behavior (average deviation of 0.019 mag) at all the epochs considered. We resolved the pole ambiguity and found the spin-vector coordinates to be within 5° of [longitude, latitude] = [30°, −16°] in the Ecliptic J2000.0 reference frame, indicating a high obliquity of about 84°, leading to high seasonal contrast. The best triaxial-ellipsoid fit returns ellipsoidal radii of , and . From the mass of Pallas determined by gravitational perturbation on other minor bodies , [Michalak, G., 2000. Astron. Astrophys. 360, 363-374], we derive a density of significantly different from the density of C-type (1) Ceres of [Carry, B., Dumas, C., Fulchignoni, M., Merline, W.J., Berthier, J., Hestroffer, D., Fusco, T., Tamblyn, P., 2008. Astron. Astrophys. 478 (4), 235-244]. Considering the spectral similarities of Pallas and Ceres at visible and near-infrared wavelengths, this may point to fundamental differences in the interior composition or structure of these two bodies.We define a planetocentric longitude system for Pallas, following IAU guidelines. We also present the first albedo maps of Pallas covering ∼80% of the surface in K-band. These maps reveal features with diameters in the 70-180 km range and an albedo contrast of about 6% with respect to the mean surface albedo.