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Sulfur has been observed to be severely depleted in dense clouds leading to uncertainty in the molecules that contain it and the chemistry behind their evolution. Here, we aim to shed light on the sulfur chemistry in young stellar objects (YSOs) by using high-resolution infrared spectroscopy of absorption by the ν3 rovibrational band of SO2 obtained with the Echelon-Cross-Echelle Spectrograph on the Stratospheric Observatory for Infrared Astronomy. Using local thermodynamic equilibrium models we derive physical parameters for the SO2 gas in the massive YSO MonR2 IRS3. This yields a SO2/H abundance lower limit of 5.6 ± 0.5 × 10(exp -7), or >4% of the cosmic sulfur budget, and an intrinsic line width (Doppler parameter) of b < 3.20 km s(exp -1). The small line widths and high temperature (Tex = 234 ± 15 K) locate the gas in a relatively quiescent region near the YSO, presumably in the hot core where ices have evaporated. This sublimation unlocks a volatile sulfur reservoir (e.g., sulfur allotropes as detected abundantly in comet 67P/Churyumov–Gerasimenko), which is followed by SO2 formation by warm, dense gas-phase chemistry. The narrowness of the lines makes formation of SO2 from sulfur sputtered off grains in shocks less likely toward MonR2 IRS3.

We attempt to confirm bright non-local thermodynamic equilibrium (non-LTE) emission from the exoplanet HD 189733b at 3.25 microns, as recently reported by Swain et al. based on observations at low spectral resolving power (lambda/delta lambda approximately equals 30). Non-LTE emission lines from gas in an exoplanet atmosphere will not be significantly broadened by collisions, so the measured emission intensity per resolution element must be substantially brighter when observed at high spectral resolving power. We observed the planet before, during, and after a secondary eclipse event at a resolving power lambda/delta lambda equals 27,000 using the NIRSPEC spectrometer on the Keck II telescope. Our spectra cover a spectral window near the peak found by Swain et al., and we compare emission cases that could account for the magnitude and wavelength dependence of the Swain et al. result with our final spectral residuals. To model the expected line emission, we use a general non-equilibrium formulation to synthesize emission features from all plausible molecules that emit in this spectral region. In every case, we detect no line emission to a high degree of confidence. After considering possible explanations for the Swain et at., results and the disparity with our own data, we conclude that an astrophysical source for the putative non-LTE emission is unlikely. We note that the wavelength dependence of the signal seen by Swain et al. closely matches the 2(sub 1/2) band of water vapor at 300 K, and we suggest that an imperfect correction for telluric water is the source of the feature claimed by Swain et al.

We quantified eight parent volatiles (H2O, C2H6, HCN, CO, CH3OH, H2CO, C2H2, and CH4) in the Jupiter-family comet Tempel 1 using high-dispersion infrared spectroscopy in the wavelength range 2.8 to 5.0 micrometers. The abundance ratio for ethane was significantly higher after impact, whereas those for methanol and hydrogen cyanide were unchanged. The abundance ratios in the ejecta are similar to those for most Oort cloud comets, but methanol and acetylene are lower in Tempel 1 by a factor of about 2. These results suggest that the volatile ices in Tempel 1 and in most Oort cloud comets originated in a common region of the protoplanetary disk.

FYO1-FY03 Origins support to the PI had been as part of an effort involving Profs. Blake, van Dishoeck and L.G. Mundy of the University of Maryland. As outlined below, the merging of BIMA+OVRO into the Combined Array for Research in Millimeter Astronomy (CARMA) and our mutual involvement in the Spitzer Legacy Science program now provides a more natural means of continuing the Caltech/Maryland collaboration. In addition, the spectroscopy/radiative transfer programs led by Profs. Blake, Hogerheijde, and van Dishoeck form a more cohesive basis for a single proposal. Students supported by our previous Origins grant have been involved in making some of the first sub-arcsecond resolution images of the morphology and chemistry of individual YSOs at OVRO and BIMA, in the analysis of IR spectra taken by ISO, and in continuing exploratory IR diffraction-limited imaging and spectroscopy at the Keck and VLT observatories. Notable scientific accomplishments in the past grant period include: 1) detecting high density and temperature hot cores in the dynamically accreting envelopes of low mass protostars that contain significant quantities of complex, prebioitc molecules, 2) imaging chemical and isotopic zonation in the outer regions of T Tauri star accretion disks, particularly fractional ionization and D/H studies, 3) acquiring and modeling the first extensive CO v = 1 approaches 0 spectroscopy survey of the terrestrial planet-forming region of circumstellar accretion disks, and 4) optimizing detailed radiative transfer modeling of the molecular and dust emission from YSO envelopes and from comets, including a new parallelized implementation.

We present interferometric detections of HCN in comets LINEAR (C/2002 T7) and NEAT (C/2001 Q4) with the Berkeley-Illinois-Maryland Association (BIMA) Array in its D-configuration cross-correlation mode. We detected the HCN J = 1 - 0 emission line in both comets. With a 25".4 x 20".3 synthesized beam around Comet LINEAR, we found a total beam averaged HCN column density (assuming a rotation temperature of 146 K) of < N(sub T) > = 2.1(11)x 10(sup 13) cm(exp -2), and a HCN production rate of Q(HCN)=2.8(15)x 10(sup 27) s(exp -1). With a 21".3 x 17".5 synthesized beam around Comet NEAT, we found a total beam averaged HCN column density (assuming a rotation temperature of 107 K) of < N(sub T) > = 5.7(30) x 10(sup l2) cm(exp -2), and a HCN production rate of Q(HCN)=8.3(44) x 10(sup 26) s(exp -l) giving a production rate of HCN relative to H2O of approximately 0.09(5)%. The production rates relative to H2O and spatial extent of HCN are similar to previous comet observations.

We propose to develop new technologies with support provided by PIDDP that will enable the in situ measurements of abundances and stable isotope ratios in important radiatively and biogenically active gases such as carbon dioxide, carbon monoxide, water, methane, nitrous oxide, and hydrogen sulfide to very high precision (0.1 per mil or better for the isotopic ratios, for example). Such measurements, impossible at present, could provide pivotal new constraints on the global (bio)geochemical budgets of these critical species, and could also be used to examine the dynamics of atmospheric transport on Mars, Titan, and other solar system bodies. We believe the combination of solid state light sources with imaging of the IR laser induced fluorescence (IR-LIF) via newly available detector arrays will make such in situ measurements possible for the first time. Even under ambient terrestrial conditions, the LIF yield from vibrational excitation of species such as water and carbon dioxide should produce emission measures well in excess of ten billion photons/sec from samples volumes of order 1 c.c. These count rates can, in principle, yield detection limits into the sub-ppt range that are required for the in situ isotopic study of atmospheric trace gases. While promising, such technologies are relatively immature, but developing rapidly, and there are a great many uncertainties regarding their applicability to in situ IR-LIF planetary studies. We therefore feel PIDDP support will be critical to developing these new tools, and propose a three-year program to combine microchip near-IR lasers with low background detection axes and state-of-the-art HgCdTe detectors developed for astronomical spectroscopy to investigate the sensitivity of IR-LIF under realistic planetary conditions, to optimize the optical pumping and filtering schemes for important species, and to apply the spectrometer to the non-destructive measurement of stable isotopes in a variety of test samples. These studies form the necessary precursors to the development of compact, lightweight stable isotope/trace gas sensors for future planetary missions.

As described in the original proposal and in our progress reports, research in the Blake group supported by the Exobiology program seeks to understand the pre-biotic chemistry of carbon along with that of other first- and second-row elements from the earliest stages of star formation through the development of planetary systems. The major tool used is spectroscopy, and the program has observational, laboratory, and theoretical components. The observational and theoretical programs are concerned primarily with a quantitative assessment of the chemical budgets of the biogenic elements in the circumstellar environment of forming stars and planetary systems, while the laboratory work is focused on the complex species that characterize the pre-biotic chemistry of carbon. We outline below our results over the past year acquired, in part, with Exobiology support.

As described in the original proposal and in our progress reports, research in the Blake group supported by the Exobiology program seeks to understand the pre-biotic chemistry of carbon along with that of other first- and second-row elements from the earliest stages of star formation through the development of planetary systems. The major tool used is spectroscopy, and the program has observational, laboratory, and theoretical components. The observational and theoretical programs are concerned primarily with a quantitative assessment of the chemical budgets of the biogenic elements in star-forming molecular cloud cores, while the laboratory work is focused on the complex species that characterize the prebiotic chemistry of carbon. We outline below our results over the past two years acquired, in part, with Exobiology support.

Temperature-dependent near-IR photodissociation spectra were obtained for several vibrational overtone transitions of peroxynitric acid (HNO4) with a tunable OPO photolysis/OH laser-induced-fluorescence system. Band-integrated photodissociation cross-sections (definity integral of sigma(sub diss)), determined relative to that for the 3nu(sub 1), OH stretching overtone, were measured for three dissociative bands. Assuming unit quantum efficiency for photodissociation of 3nu(sub 1), we find 2nu(sub 1) + nu(sub 3)(8242/cm) = (1.21 x 10(exp -20) (independent of temperature), 2nu(sub 1) (6900/cm) = 4.09 x 10(exp 18) * e(sup (-826,5/T)) (295 K greater than T greater than 224 K), and nu(sub 1) + 2nu(sub 3) (6252/cm) = 1.87 x 10(exp -19) * e(sup (- 1410.7/T)) (278 K greater than T greater than 240 K) sq cm/molecule cm. The photodissociation cross-sections are independent of pressure over the range 2 to 40 Torr. Temperature-dependent quantum yields (phi) for these transitions were obtained using integrated absorption cross-sections (definity integral of sigma(sub abs)) of HNO4 overtone vibrations measured with a FTIR spectrometer. In the atmosphere, photodissociation in the infrared is dominated by excitation of the first overtone of the OH stretching vibration (2nu((sub 1)). Inclusion of all dissociative HNO4 overtone and combination transitions yields a daytime IR photolysis rate of approximately 1 x 10(esp -1)/s. This process significantly shortens the estimated lifetime of HNO4 in the upper troposphere and lower stratosphere.

We review the chemical processes that are important in the evolution from a molecular cloud core to a protostellar disk. These cover both gas phase and gas grain interactions. The current observational and theoretical state of this field are discussed.

Molecular line surveys and fully sampled spectral line maps at 1.3 and 0.87 mm are used to examine the physical and chemical characteristics of the extreme Class I sources IRAS 4A and 4B in the L1450/NGC 1333 molecular cloud complex. A very well collimated, jetlike molecular flow emanates from IRAS 4A, with a dynamical age of a few thousand years. Symmetric, clumpy structure along the outflow lobes suggests that there is considerable variability in the mass-loss rate or wind velocity even at this young age. Molecular emission lines toward IRAS 4A and 4B are observed to be weak in the velocity range corresponding to quiescent material surrounding the young stellar objects (YSOs). Depletion factors of 10-20 are observed for all molecules, including CO, even for very conservative mass estimates from the measured millimeter and submillimeter dust continuum. However, abundance scaled with respect to CO are similar to other dark molecular cloud cores. Such depletions could be mimicked by high dust and optical depths or increased grain emissivities at the observing frequencies of 230 and 435 GHz, but the millimeter and submillimeter spectral energy distributions suggest that this is unlikely over the single-dish size scales of 5000-10,000 AU. Dense, outflowing gas is found to be kinematically, but not spatially, distinct from the quiescent material on these size scales. If CO is used as a chemical standard for the high-velocity gas, we find substantial enhancements in abundances of several molecules in outflowing material, most notably CS, SIO, and CH3OH. The SiO emission is kinematically well displaced from the bulk cloud velocity and likely arises from directly shocked material. As is the case for CO, however, the outflow features from more volatile species are centered near the cloud velocity and are often characterized by quite low rotational temperatures. We suggest that grain-grain collisions induced by velocity shear zones surrounding the outflow axes transiently desorb the grain mantles, resulting in large abundance enhancements of selected species. Similar results have recently been obtained in several other low-mass YSOs, where outflowing gas is often both kinematically and spatailly distinct, and are illustrative of the ability of accretion and outflow processes to simultaneously modify the composition of the gas and dust surrounding young stars.

Results from millimeter and submillimeter spectral line surveys of the protobinary source Infrared Astronomical Satellite (IRAS) 16293-2422 are presented. Here we outline the abundances of silicon- and sulfur-containing species. A combination of rotation diagram and full statistical equilibrium/radiative transfer calculations is used to constrain the physical conditions toward IRAS 16293 and to construct its beam-averaged chemical composition over a 10 to 20 sec (1600 to 3200 AU) scale. The chemical complexity as judged by species such as SiO, OCS, and H2S, is intermediate between that of dark molecular clouds such as L134N and hot molecular cloud cores such as Orion KL. From the richness of the spectra compared to other young stellar objects of similar luminosity, it is clear that molecular abundances do not scale simply with mass; rather, the chemistry is a strong function of evolutionary state, i.e., age.

High spectral and spatial resolution observations of the HCO(+) molecule toward the T Tau binary system obtained with the Owens Valley Millimeter Array reveal a broad emission line profile (V(sub LSR) = 7.2 km s(exp -1), Delta V = 2.0 km s(exp -1)) upon which a narrow, redshifted absorption feature (V(sub LSR) = 8.5 km s(exp -1), Delta V approximately equals 0.5 km s(exp -1)) is superposed. One possible interpretation of the absorption is that it rises from infall of molecular cloud envelope material onto the immediate circumbinary region, which would imply that large-scale dynamic accretion processes are still active well into the optically visible stages of star formation. Provided the mass is deposited at radii sufficiently close to the young stars, estimates of the accretion rates indicate that infall may add enough material to the system to account for the FU Orionis type flares recently observed in T Tau in approximately less than 100 yr.

High resolution (approximately 4 sec) aperture synthesis maps of the CO (1 yields 0), (13)CO (1 yields 0), (13)CO (2 yields 1), and asociated continuum emission from the FU Orions candidate V1331 Cygni reveal a massive, 0.5 +/- 0.15 solar mass, circumstellar disk surrounded by a flattened gaseous envelope, 6000 x 4400 AU in size, mass greater than or equal to 0.32 solar mass. These images and lower resolution measurements also trace a bipolar outflow and gaseous ring, 4.1 by 2.8 x 10(exp 4) AU, mass greater than or equal to 0.07 solar mass, radially expanding at 22 +/- 4 km/s. We suggest this ring is a swept-up gaseous torus from an energetic mass ejection stage, possibly an FU Orionis outburst or outburts, approximately 4 x 10(exp 3) yr ago that imparted greater than or equal to 10(exp 45) ergs into the ambient cloud.

High-resolution optical and microwave spectra of the gas-phase benzene-ammonia dimer were obtained, showing that the ammonia molecule resides above the benzene plane and undergoes free, or nearly free, internal rotation. To estimate the binding energy (De) and other global properties of the intermolecular potential, theoretical calculations were performed for the benzene-ammonia dimer, using the Gaussian 92 (Fritsch, 1992) program at the MP2/6-31G** level. The predicted De was found to be at the lowest end of the range commonly accepted for hydrogen bonding and considerably below that of C6H6-H2O, consistent with the gas-phase acidities of ammonia and water. The observed geometry greatly resembles the amino-aromatic interaction found naturally in proteins.

We present interferometric observations of the SiO J = 2-1, H13CO(+) J = 1-0, HC3N J = 11-10, CH3OH J(K) = 2(0)-1(0), and SO2 J(KpK0) = 8(17)-8(08) transitions along with the 3.1 mm continuum toward the young stellar object Orion S. The HC3N and H13CO(+) emission trace similar spatial and velocity distributions which are extended and follow the Orion molecular ridge. The SiO emission is more spatially confined, peaking to the west of the 3.1 mm continuum source, while the CH3OH emission peaks to the southwest. Weak SO2 emission was detected southeast of the continuum source position. Column densities and fractional abundances are derived for each species at different positions in the region. In general, the molecular abundances near the continuum source are similar to those in the quiescent material near IRc 2, but the abundances decrease toward the continuum source position indicating localized depletions of at least a factor of three. The presence of strong SiO emission with much weaker SO2 emission is interpreted as resulting from high-velocity shock interactions between the outflow from Orion S and the surrounding cloud.

High spatial and spectral resolution dust continuum and CS line-emission maps of the material immediately surrounding HL Tauri are presented. The 3.06-thermal dust map gives an upper limit to the source size of roughly 200 AU. When combined with previous millimeter continuum measurements, a beta value of 1.2 +/-0.3 is derived along with a disk mass of 0.1 solar mass, in agreement with previous disk radiative transfer models of the IR and submillimeter flux from HL Tau. The low dust emissivity index as compared to particles in the diffuse ISM is best explained by grain growth or composition evolution. The present observations of the CS and CO emission lines forming the molecular cloud surrounding HL Tauri are consistent with the 'canonical' temperatures, densities, and abundances derived in other Taurus cloud cores. In contrast, the CS emission in aperture synthesis maps at 650-AU spatial resolution is most consistent with CS/CO ratios at least 25-50 times lower in the gas immediately surrounding HL Tauri if the CS emission is optically thin. The continuum and spectral line results obtained are strong indicators of conditions thought to be similar to those in the presolar nebula some 4.5 AE ago.

A submillimeter survey of Sgr B2 is described in which sufficient spatial resolution permitted the observation of some of the source structure. The position Sgr B2(M) is examined in relation to the submillimeter emission of Sgr B2(N) and previous millimeter observational data of source (M) at a lower spatial resolution. Because the submillimeter observations are more sensitive to core emission, the molecules SO2 and CH3OH tend to dominate the spectrum. The core emission is found to be similar to that of the Orion molecular cloud, and the submillimeter and millimeter lines have high optical depths. The (N) source has a much higher column density than that of (M) except for SO and SO2, and (N) also appears to have a higher excitation which can indicate a core with a higher density.

For the most part, gas phase models of the chemistry of dense molecular clouds predict the abundances of simple species rather well. However, for larger molecules and even for small systems rich in carbon these models often fail spectacularly. Researchers present a brief review of the basic assumptions and results of large scale modeling of the carbon chemistry in dense molecular clouds. Particular attention is to the influence of the gas phase C/O ratio in molecular clouds, and the likely role grains play in maintaining this ratio as clouds evolve from initially diffuse objects to denser cores with associated stellar and planetary formation. Recent spectral line surveys at centimeter and millimeter wavelengths along with selected observations in the submillimeter have now produced an accurate inventory of the gas phase carbon budget in several different types of molecular clouds, though gaps in our knowledge clearly remain. The constraints these observations place on theoretical models of interstellar chemistry can be used to gain insights into why the models fail, and show also which neglected processes must be included in more complete analyses. Looking toward the future, larger molecules are especially difficult to study both experimentally and theoretically in such dense, cold regions, and some new methods are therefore outlined which may ultimately push the detectability of small carbon chains and rings to much heavier species.

Emission from the 492 GHz lines of C I have been observed toward six positions in the Ophiuchus molecular cloud complex for which accurate visual extinctions are available. The column density of C I increases with A(V) to greater than 2 x 10 to the 17th/sq cm at 100 mag, the column-averaged fractional abundance reaches a peak of about 2.2 x 10 to the -5th for A(V) in the range 4-11 mag and the column-averaged abundance ratio of C I to CO decreases with A(V) from about 1 at 2 mag to greater that about 0.03 at 100 mag. These results imply that, while C I is not the primary reservoir of gaseous carbon even at cloud edges, its fractional abundance remains high for at least 10 mag into the cloud and may be significant at even greater depths.

The 3P1 yields 3P0 line of neutral C I toward Z Oph was observed at 492 GHz to demonstrate that C I column densities and line velocity measurements can be made with both submillimeter and UV techniques. The data were collected with an InSb cyclotron-resonance heterodyne receiver on the NASA Kuiper Airborne Observatory at an altitude of 12.5 km. The radio data densities were compared with densities calculated from Copernicus satellite UV data. It was found that the radio data densities improved that accuracy of column densities previously determined from UV measurements. It is concluded that follow-up high resolution submillimeter data are a useful aid in the interpretation of UV data on column densities.