Context. Ammonia and its deuterated isotopologues probe physical conditions in dense molecular cloud cores. The time-dependence of deuterium fractionation and the relative abundances of different nuclear spin modifications are supposed to provide a means of determining the evolutionary stages of these objects. Aims. We aim to test the current understanding of spin-state chemistry of deuterated species by determining the abundances and spin ratios of NH2D, NHD2 and ND3 in a quiescent, dense cloud. Methods. Spectral lines of NH3, NH2D, NHD2, ND3 and N2D+ were observed towards a dense, starless core in Ophiuchus with the APEX, GBT and IRAM 30-m telescopes. The observations were interpreted using a gas-grain chemistry model combined with radiative transfer calculations. The chemistry model distinguishes between the different nuclear spin states of light hydrogen molecules, ammonia and their deuterated forms. Different desorption schemes can be considered. Results. High deuterium fractionation ratios with NH2D = NH3 similar to 0 : 4, NHD2 = NH2D similar to 0 : 2 and ND3 = NHD2 similar to 0 : 06 are found in the core. The observed ortho/para ratios of NH2D and NHD2 are close to the corresponding nuclear spin statistical weights. The chemistry model can approximately reproduce the observed abundances, but consistently predicts too low ortho/para-NH2D, and too large ortho/para-NHD2 ratios. The longevity of N2H+ and NH3 in dense gas, which is prerequisite to their strong deuteration, can be attributed to the chemical inertia of N-2 on grain surfaces. Conclusions. The discrepancies between the chemistry model and the observations are likely to be caused by the fact that the model assumes complete scrambling in principal gas-phase deuteration reactions of ammonia, which means that all the nuclei are mixed in reactive collisions. If, instead, these reactions occur through proton hop/hydrogen abstraction processes, statistical spin ratios are to be expected. The present results suggest that while the deuteration of ammonia changes with physical conditions and time, the nuclear spin ratios of ammonia isotopologues do not probe the evolutionary stage of a cloud.

Pure rotational spectra of the rare isotopologues of titanium oxide, (TiO)-Ti-46, (TiO)-Ti-47, (TiO)-Ti-49, and (TiO)-Ti-50, have been recorded using a combination of Fourier transform millimeter-wave (FTmmW) and millimeter/submillimeter direct absorption techniques in the frequency range 62-538 GHz. This study is the first complete spectroscopic characterization of these species in their X-3 Delta(r) ground electronic states. The isotopologues were created by the reaction of N2O or O-2 and titanium vapor, produced either by laser ablation or in a Broida-type oven, and observed in the natural Ti isotopic abundances. Between 10 and 11 rotational transitions J + 1 <-> J were measured for each species, typically in all 3 spin-orbit ladders Omega-1,2, and 3. For (TiO)-Ti-47 and (TiO)-Ti-49, hyperfine structure was resolved, originating from the titanium-47 and titanium-49 nuclear spins of I = 5/2 and 7/2, respectively. For the Omega = 1 and 3 components, the hyperfine structure was found to follow a classic Lande pattern, while that for Omega = 2 appeared to be perturbed, likely a result of mixing with the nearby isoconfigurational a(1)Delta state. The spectra were analyzed with a case (a) Hamiltonian, and rotational, spin-orbit, and spin-spin parameters were determined for each species, as well as magnetic hyperfine and electric quadrupole constants for the two molecules with nuclear spins. The most abundant species, (TiO)-Ti-48, has been detected in circumstellar envelopes. These measurements will enable other titanium isotopologues to be studied at millimeter wavelengths, providing Ti isotope ratios that can test models of nucleosynthesis.

We report the second complete molecular line data release from the Census of High-and Medium-mass Protostars (CHaMP), a large-scale, unbiased, uniform mapping survey at sub-parsec resolution, of millimeter-wave line emission from 303 massive, dense molecular clumps in the Milky Way. This release is for all (CO)-C-12 J = 1 -> 0 emission associated with the dense gas, the first from Phase II of the survey, which includes (CO)-C-12, (CO)-C-13, and (CO)-O-18. The observed clump emission traced by both (CO)-C-12 and HCO+ (from Phase I) shows very similar morphology, indicating that, for dense molecular clouds and complexes of all sizes, parsec-scale clumps contain. similar to 75% of the mass, while only 25% of the mass lies in extended (>10 pc) or "low density" components in these same areas. The mass fraction of all gas above a density of 10(9) m(-3) is xi(9) greater than or similar to 50%. This suggests that parsec-scale clumps may be the basic building blocks of the molecular interstellar medium, rather than the standard GMC concept. Using (CO)-C-12 emission, we derive physical properties of these clumps in their entirety, and compare them to properties from HCO+, tracing their denser interiors. We compare the standard X-factor converting I (CO)-C-12 to N-H2 with alternative conversions, and show that only the latter give whole-clump properties that are physically consistent with those of their interiors. We infer that the clump population is systematically closer to virial equilibrium than when considering only their interiors, with perhaps half being long-lived (10s of Myr), pressure-confined entities that only terminally engage in vigorous massive star formation, supporting other evidence along these lines that was previously published.

We sort 4683 molecular clouds between 10 degrees < l < 65 degrees from the Bolocam Galactic Plane Survey based on observational diagnostics of star formation activity: compact 70 mu m sources, mid-IR color-selected YSOs, H2O and CH3OH masers, and UCH II. regions. We also present a combined NH3-derived gas kinetic temperature and H2O maser catalog for 1788 clumps from our own GBT 100 m observations and from the literature. We identify a subsample of 2223 (47.5%) starless clump candidates (SCCs), the largest and most robust sample identified from a blind survey to date. Distributions of flux density, flux concentration, solid angle, kinetic temperature, column density, radius, and mass show strong (>1 dex) progressions when sorted by star formation indicator. The median SCC is marginally subvirial (alpha similar to 0.7) with >75% of clumps with known distance being gravitationally bound (alpha < 2). These samples show a statistically significant increase in the median clump mass of Delta M similar to 170-370 M-circle dot from the starless candidates to clumps associated with protostars. This trend could be due to (i) mass growth of the clumps at (M) over dot similar to 200-440 M-circle dot Myr(-1) for an average freefall 0.8 Myr timescale, (ii) a systematic factor of two increase in dust opacity from starless to protostellar phases, and/or (iii). a variation in the ratio of starless to protostellar clump lifetime that scales as similar to M-0.4. By comparing to the observed number of CH3OH maser containing clumps, we estimate the phase. lifetime of massive (M > 10(3) M-circle dot) starless clumps to be 0.37 +/- 0.08 Myr (M/10(3) M-circle dot)(-1); the majority (M < 450 M-circle dot) have phase. lifetimes longer than their average freefall time.

New detections of HNC have been made toward 11 planetary nebulae (PNe), including K4-47, K3-58, K3-17, M3-28, and M4-14. These sources, which represent a wide range of ages and morphologies, had previously been observed in HCN by Schmidt & Ziurys. Measurements of the J = 1 -> 0 and J = 3 -> 2 transitions of HNC near 90 and 271 GHz were conducted using the new 12 m and the Sub-Millimeter Telescope of the Arizona Radio Observatory. HCN and HNC were also identified via their J = 1 -> 0 lines toward eight positions across the Helix Nebula (NGC 7293). Column densities for HNC, determined from radiative transfer modeling, were N-tot(HNC) similar to (0.06-4.0) x 10(13) cm(-2), corresponding to fractional abundances with respect to H-2 of f similar to (0.02-1.4) x 10(-7). The HCN and HNC column densities across the Helix were found to be N-tot (HCN) similar to (0.2-2.4). x. 10(12) cm(-2) and Ntot (HNC) similar to (0.07-1.6). x. 1012 cm(-2), with fractional abundances of (0.2-3.2) x 10(-7) and (0.09-2.2) x 10(-7). The [ HCN]/[ HNC] ratio varied between similar to 1-8 for all PNe, with [ HCN]/[ HNC] similar to 1-4 across the Helix. These values are greatly reduced from what has been found in asymptotic giant branch stars, where the ratio is typically > 100. Both the abundance of HNC and the [ HCN]/[ HNC] ratio do not appear to vary significantly with nebular age across a time span of similar to 10,000 years, in contrast to predictions of chemical models. The increase in HNC appears to arise in the proto-planetary stage, but becomes " frozen" once the PN phase is reached.

New laboratory measurements of hydrides have been carried out using terahertz direct absorption spectroscopy. Spin components of the N = 2 <- 1 transition of the free radical CrH (X (6)Sigma(+)) have been recorded in the range 730-734 GHz, as well as a new measurement of the J = 2 <- 1 line of AlH (X (1)Sigma(+)) near 755 GHz. Both species were created in an AC discharge of H-2, argon, and metal vapor. For CrH, the chromium source was Cr(CO)(6), while AlH was produced from Al(CH3)3. The J = 4.5 <- 3.5 and 3.5 <- 2.5 fine-structure components were recorded for CrH, each which consists of resolved proton hyperfine doublets. For AlH, the two main quadrupole components, F = 4.5 <- 3.5 and 3.5 <- 2.5, of the J = 2 <- 1 transition were observed as blended features. These data were analyzed with previous 1 <- 0 millimeter/submillimeter measurements with (6)Sigma and (1)Sigma Hamiltonians for chromium and aluminum hydrides, respectively, and rotational, fine-structure (CrH only), and hyperfine constants were derived. The new measurements have resulted in refined spectroscopic parameters for both species, as well as direct measurement of the respective 2 <- 1 rotational transitions. This work also resolves a 10 MHz discrepancy in the frequency of the AlH line. CrH and AlH have already been observed in the photospheres of stars via their electronic transitions. These data will facilitate their discovery at submillimeter/terahertz wavelengths in circumstellar envelopes and perhaps in diffuse clouds.

We revisit the proposed extended Schmidt law, which posits that the star formation efficiency in galaxies depends on the stellar mass surface density, by investigating spatially resolved star formation rates (SFRs), gas masses, and stellar masses of star formation regions in a vast range of galactic environments, from the outer disks of dwarf galaxies, to spiral disks and to merging galaxies, as well as individual molecular clouds in M33. We find that these regions are distributed in a tight power law as Sigma(SFR) proportional to (Sigma(0.5)(star)Sigma(gas))(1.09), which is also valid for the integrated measurements of disk and merging galaxies at high-z. Interestingly, we show that star formation regions in the outer disks of dwarf galaxies with Sigma(SFR) down to 10(-5) M(circle dot)yr(-1) kpc(-2), which are outliers of both the Kennicutt-Schmidt and Silk-Elmegreen laws, also follow the extended Schmidt law. Other outliers in the Kennicutt-Schmidt law, such as extremely metal-poor star formation regions, also show significantly reduced deviation from the extended Schmidt law. These results suggest an important role for existing stars in helping to regulate star formation through the effect of their gravity on the midplane pressure in a wide range of galactic environments.

We present Herschel Spectral and Photometric Imaging Receiver (SPIRE)-Fourier Transform Spectrometer (FTS) intermediate-sampled mapping observations of the central similar to 8 kpc (similar to 150 arcsec) of M51, with a spatial resolution of 40 arcsec. We detect four (CO)-C-12 transitions (J = 4-3 to J = 7-6) and the [C i] P-3(2)-P-3(1) and P-3(1)-P-3(0) transitions. We supplement these observations with ground-based observations of (CO)-C-12 J = 1-0 to J = 3-2 and perform a two-component non-local thermodynamic equilibrium analysis. We find that the molecular gas in the nucleus and centre regions has a cool component (T-kin similar to 10-20 K) with a moderate but poorly constrained density (n(H-2) similar to 10(3)-10(6) cm(-3)), as well as significant molecular gas in a warmer (T-kin similar to 300-3000 K), lower density (n(H-2) similar to 10(1.6)-10(2.5) cm(-3)) component. We compare our CO line ratios and calculated densities along with ratios of CO to total infrared luminosity to a grid of photon-dominated region (PDR) models and find that the cold molecular gas likely resides in PDRs with a field strength of G(0) similar to 10(2). The warm component likely requires an additional source of mechanical heating, from supernovae and stellar winds or possibly shocks produced in the strong spiral density wave. When compared to similar two-component models of other star-forming galaxies published as part of the Very Nearby Galaxies Survey (Arp 220, M82 and NGC 4038/39), M51 has the lowest density for the warm component, while having a warm gas mass fraction that is comparable to those of Arp 220 and M82, and significantly higher than that of NGC 4038/39.

New detections of CCH have been made toward nine planetary nebulae (PNe), including K4-47, K3-58, K3-17, M3-28, and M4-14. Measurements of the N = 1 -> 0 and N = 3 -> 2 transitions of this radical near 87 and 262 GHz were carried out using the new 12 m and the Sub-Millimeter Telescope (SMT) of the Arizona Radio Observatory (ARO). The presence of fine and/or hyperfine structure in the spectra aided in the identification. CCH was not observed in two PNe which are sources of C-60. The planetary nebulae with positive detections represent a wide range of ages and morphologies, and all had previously been observed in HCN and HNC. Column densities for CCH in the PNe, determined from radiative transfer modeling, were N-tot(CCH) similar to 0.2-3.3 x 10(15) cm(-2), corresponding to fractional abundances with respect to H-2 of f similar to 0.2-47 x 10(-7). The abundance of CCH was found to not vary significantly with kinematic age across a time span of similar to 10,000 years, in contrast to predictions of chemical models. CCH appears to be a fairly common constituent of PNe that are carbon-rich, and its distribution may anti-correlate with that of C-60. These results suggest that CCH may be a product of C-60 photodestruction, which is known to create C-2 units. The molecule may subsequently survive the PN stage and populate diffuse clouds. The distinct, double-horned line profiles for CCH observed in K3-45 and M3-28 indicate the possible presence of a bipolar flow oriented at least partially toward the line of sight.

We present a measurement of the abundance of carbon monoxide in the early universe, utilizing the final results from the CO Power Spectrum Survey (COPSS). Between 2013 and 2015, we performed observations with the Sunyaev-Zel'dovich Array to measure aggregate CO emission from z similar to 3 galaxies with the intensity mapping technique. Data were collected on 19 fields, covering an area of 0.7 square degrees, over the frequency range 27-35 GHz. With these data, along with data analyzed in COPSS I, we are able to observe the CO(1-0) transition within the redshift range z = 2.3-3.3 for spatial frequencies between k = 0.5-10 h Mpc(-1), spanning a comoving volume of 4.9 x 10(6) h(-3) Mpc(3). We present estimates of contributions from continuum sources and ground illumination within our measurement. We constrain the amplitude of the CO power spectrum to P-CO = 3.0(-1.3)(+1.3) x 10(3) mu K-2(h(-1) Mpc)(3), or Delta(2)(CO)(k=1 h Mpc(-1)) = 1.5(-0.7)(+0.7) x 10(3) mu K-2, at 68% confidence, and PCO > 0 at 98.9% confidence. These results are a factor of 10 improvement in sensitivity compared to those of COPSS I. With this measurement, we constrain on the CO(1-0) galaxy luminosity function at z similar to 3. Assuming that CO emission is proportional to halo mass and using theoretical estimates of the scatter in this relationship, we constrain the ratio of CO(1-0) luminosity to halo mass to A(CO) = 6.3(-2.1)(+1.4) x 10 (7) L circle dot M circle dot-1. Assuming a Milky Way-like linear relationship between CO luminosity and molecular gas mass, we estimate a mass fraction of molecular gas of f(H2) = 5.5(-2.2)(+3.4) x 10(-2) for halos with masses of similar to 10(12)M(circle dot). Using theoretical estimates for the scaling of molecular gas mass fraction and halo mass, we estimate the cosmic molecular gas density to be rho(z similar to 3) (H-2) = 1.1(-0.4)(+0.7) x 10(8) M(circle dot)Mpc(-3).