Supersonic jet chirped pulse microwave spectroscopy of ring-like methanol : water pentamers.

The potential energy surfaces of pure methanol and mixed methanol-water pentamers have been explored using chirped pulse Fourier-transform microwave spectroscopy aided by ab initio calculations. Rotational constants, anharmonic corrections, dipole moments, and relative energies were calculated for different conformers. Predicted rotational transitions were then fit to experimental spectra from 10-18 GHz and the assignments were confirmed using double resonance experiments where feasible. The results show all 23 of the lowest energy conformers are bound in a planar ring of hydrogen bonding that display a steady decrease in the RO-O distance along this ring as methanol content is increased. Interspersed methanol and water conformers have comparable relative abundances to those with micro-aggregation, but structures with micro-aggregated methanol and water have a higher rigid rotor fitting error. The computational methods' high degree of accuracy when compared to our experimental results suggests the strong donor-acceptor hydrogen bonding in these clusters leads to well-defined minima on the intermolecular potential energy surface.

Chirped pulse Fourier-transform microwave spectroscopy of alcohol and water tetramers.

In an effort to build towards quantitative models of alcohol:water microaggregation in liquid mixtures, the present works characterizes the energy landscape and structures of pure ethanol and mixed ethanol:water tetramers using Chirped Pulse Fourier-transform Microwave spectroscopy. Many conformers of each type of tetramer are available, and those with sufficiently strong dipole moments are experimentally examined. This analysis considers, but does not explicitly fit, the splitting of rotational states due to internal rotation of the methyl groups present, as well as utilizes isotopic substitution experiments to verify the conformer variations observed. Implications of the listed results include a suggestion of the stability of micro-aggregated structures as opposed to homogeneously mixed clusters, informing future work on characterization of larger clusters and any potential modeling of the hydrogen bond network at play.

High throughput chirped pulse Fourier-transform microwave spectroscopy of ethanol and water clusters.

Here we discuss the design and performance of a novel high-throughput instrument for Chirped Pulse Fourier-transform Microwave (CP-FTMW) spectroscopy, and demonstrate its efficacy through the identification of the lowest energy conformers of the ethanol trimer and mixed water : ethanol trimers. Rotational constants for these trimers were calculated from observed lines in the spectra from 10 to 14 GHz, and compared to the results of anharmonic ab initio computations. As predicted, all trimers share a cyclic donor-acceptor hydrogen bonding structure, with the ethanol monomer favoring the gauche conformation in the lowest energy structures. The increased speed of data collection and resulting sensitivity opens a new avenue into rotational studies of higher order clusters.

Earth's carbon deficit caused by early loss through irreversible sublimation.

Carbon is an essential element for life, but its behavior during Earth's accretion is not well understood. Carbonaceous grains in meteoritic and cometary materials suggest that irreversible sublimation, and not condensation, governs carbon acquisition by terrestrial worlds. Through astronomical observations and modeling, we show that the sublimation front of carbon carriers in the solar nebula, or the soot line, moved inward quickly so that carbon-rich ingredients would be available for accretion at 1 astronomical unit after the first million years. On the other hand, geological constraints firmly establish a severe carbon deficit in Earth, requiring the destruction of inherited carbonaceous organics in the majority of its building blocks. The carbon-poor nature of Earth thus implies carbon loss in its precursor material through sublimation within the first million years.

Spectroscopic constraints on CH3OH formation: CO mixed with CH3OH ices towards young stellar objects.

The prominent infrared absorption band of solid CO - commonly observed towards young stellar objects (YSOs) - consists of three empirically determined components. The broad 'red component' (2136 cm-1, 4.681 µm) is generally attributed to solid CO mixed in a hydrogen-bonded environment. Usually, CO embedded in the abundantly present water is considered. However, CO:H2O mixtures cannot reproduce the width and position of the observed red component without producing a shoulder at 2152 cm-1, which is not observed in astronomical spectra. Cuppen et al. showed that CO:CH3OH mixtures do not suffer from this problem. Here, this proposition is expanded by comparing literature laboratory spectra of different CO-containing ice mixtures to high-resolution (R = λ/Δλ = 25000) spectra of the massive YSO AFGL 7009S and of the low-mass YSOL1489 IRS. The previously unpublished spectrum of AFGL 7009S shows a wide band of solid 13CO, the first detection of 13CO ice in the polar phase. In this source, both the 12CO and 13CO ice bands are well fitted with CO:CH3OH mixtures, while respecting the profiles and depths of the methanol bands at other wavelengths, whereas mixtures with H2O cannot. The presence of a gradient in the CO:CH3OH mixing ratio in the grain mantles is also suggested. Towards L1489 IRS, the profile of the 12CO band is also better fitted with CH3OH-containing ices, although the CH3OH abundance needed is a factor of 2.4 above previous measurements. Overall, however, the results are reasonably consistent with models and experiments about formation of CH3OH by the hydrogenation of CO ices.

THz and mid-IR spectroscopy of interstellar ice analogs: methyl and carboxylic acid groups.

A fundamental problem in astrochemistry concerns the synthesis and survival of complex organic molecules (COMs) throughout the process of star and planet formation. While it is generally accepted that most complex molecules and prebiotic species form in the solid phase on icy grain particles, a complete understanding of the formation pathways is still largely lacking. To take full advantage of the enormous number of available THz observations (e.g., Herschel Space Observatory, SOFIA, and ALMA), laboratory analogs must be studied systematically. Here, we present the THz (0.3-7.5 THz; 10-250 cm(-1)) and mid-IR (400-4000 cm(-1)) spectra of astrophysically-relevant species that share the same functional groups, including formic acid (HCOOH) and acetic acid (CH3COOH), and acetaldehyde (CH3CHO) and acetone ((CH3)2CO), compared to more abundant interstellar molecules such as water (H2O), methanol (CH3OH), and carbon monoxide (CO). A suite of pure and mixed binary ices are discussed. The effects on the spectra due to the composition and the structure of the ice at different temperatures are shown. Our results demonstrate that THz spectra are sensitive to reversible and irreversible transformations within the ice caused by thermal processing, suggesting that THz spectra can be used to study the composition, structure, and thermal history of interstellar ices. Moreover, the THz spectrum of an individual species depends on the functional group(s) within that molecule. Thus, future THz studies of different functional groups will help in characterizing the chemistry and physics of the interstellar medium (ISM).

Substantial reservoirs of molecular hydrogen in the debris disks around young stars.

Circumstellar accretion disks transfer matter from molecular clouds to young stars and to the sites of planet formation. The disks observed around pre-main-sequence stars have properties consistent with those expected for the pre-solar nebula from which our own Solar System formed 4.5 Gyr ago. But the 'debris' disks that encircle more than 15% of nearby main-sequence stars appear to have very small amounts of gas, based on observations of the tracer molecule carbon monoxide: these observations have yielded gas/dust ratios much less than 0.1, whereas the interstellar value is about 100 (ref. 9). Here we report observations of the lowest rotational transitions of molecular hydrogen (H2) that reveal large quantities of gas in the debris disks around the stars beta Pictoris, 49 Ceti and HD135344. The gas masses calculated from the data are several hundreds to a thousand times greater than those estimated from the CO observations, and yield gas/dust ratios of the same order as the interstellar value.

The faint young Sun paradox: an observational test of an alternative solar model.

We report the results of deep observations at radio (3.6 cm) wavelengths of the nearby solar-type star pi 01 Ursa Majoris with the Very Large Array (VLA) intended to test an alternative theory of solar luminosity evolution. The standard model predicts a solar luminosity only 75% of the present value and surface temperatures below freezing on Earth and Mars at 4 Ga, seemingly in conflict with geologic evidence for liquid water on these planets. An alternative model invokes a compensatory mass loss through a declining solar wind that results in a more consistent early luminosity. The free-free emission from an enhanced wind around nearby young Sun-like stars should be detectable at microwave frequencies. Our observations of pi 01 UMa, a 300 million year-old solar-mass star, place an upper limit on the mass loss rate of 4-5 x 10(-11) M(solar) yr-1. Total mass loss from such a star over 4 Gyr would be less than 6%. If this star is indeed an analog of the early Sun, it casts doubt on the alternative model as a solution to the faint young Sun paradox, particularly for Mars.

Sublimation from icy jets as a probe of the interstellar volatile content of comets.

Comets are some of the most primitive bodies left over from the Solar System's early history. They may preserve both interstellar material and material from the proto-solar nebula, and so studies of their volatile components can provide clues about the evolution of gases and ices, as a collapsing molecular cloud transforms into a mature planetary system. Previous observations of emission from rotational transitions in molecules have averaged over large areas of the inner coma, and therefore include both molecules that sublimed from the nucleus and those that result from subsequent chemical processes in the coma Here we present high-resolution observations of emission from the molecules HNC, DCN and HDO associated with comet Hale-Bopp. Our data reveal arc-like structures-icy jets-offset from (but close to) the nucleus. The measured abundance ratios on 1-3" scales are substantially different from those on larger scales, and cannot be accounted for by models of chemical processes in the coma; they are, however, similar to the values observed in the cores of dense interstellar clouds and young stellar objects. We therefore propose that sublimation from millimetre-sized icy grains ejected from the nucleus provides access to relatively unaltered volatiles. The D/H ratios inferred from our data suggest that, by mass, Hale-Bopp (and by inference the outer regions of the early solar nebula) consists of > or =15-40% of largely unprocessed interstellar material.

Envelope structure of deeply embedded young stellar objects in the Serpens Molecular Cloud.

Aperture-synthesis and single-dish (sub-) millimeter molecular-line and continuum observations reveal in great detail the envelope structure of deeply embedded young stellar objects (SMM 1 = FIRS 1, SMM 2, SMM 3, SMM 4) in the densely star-forming Serpens Molecular Cloud. SMM 1, 3, and 4 show partially resolved (>2" = 800 AU) continuum emission in the beam of the Owens Valley Millimeter Array at lambda = 3.4-1.4 mm. The continuum visibilities accurately constrain the density structure in the envelopes, which can be described by a radial power law with slope -2.0 +/- 0.5 on scales of 300 to 8000 AU. Inferred envelope masses within a radius of 8000 AU are 8.7, 3.0, and 5.3 Msolar for SMM 1, 3, and 4, respectively. A point source with 20%-30% of the total flux at 1.1 mm is required to fit the observations on long baselines, corresponding to warm envelope material within approximately 100 AU or a circumstellar disk. No continuum emission is detected interferometrically toward SMM 2, corresponding to an upper limit of 0.2 Msolar assuming Td = 24 K. The lack of any compact dust emission suggests that the SMM 2 core does not contain a central protostar. Aperture-synthesis observations of the 13CO, C18O, HCO+, H13CO+, HCN, H13CN, N2H+ 1-0, SiO 2-1, and SO 2(2)-1(1) transitions reveal compact emission toward SMM 1, 3, and 4. SMM 2 shows only a number of clumps scattered throughout the primary field of view, supporting the conclusion that this core does not contain a central star. The compact molecular emission around SMM 1, 3, and 4 traces 5"-10" (2000-4000 AU) diameter cores that correspond to the densest regions of the envelopes, as well as material directly associated with the molecular outflow. Especially prominent are the optically thick HCN and HCO+ lines that show up brightly along the walls of the outflow cavities. SO and SiO trace shocked material, where their abundances may be enhanced by 1-2 orders of magnitude over dark-cloud values. A total of 31 molecular transitions have been observed with the James Clerk Maxwell and Caltech Submillimeter telescopes in the 230, 345, 490, and 690 GHz atmospheric windows toward all four sources, containing, among others, lines of CO, HCO+, HCN, H2CO, SiO, SO, and their isotopomers. These lines show 20-30 km s-1 wide line wings, deep and narrow (1-2 km s-1) self-absorption, and 2-3 km s-1 FWHM line cores. The presence of highly excited lines like 12CO 4-3 and 6-5, 13CO 6-5, and several H2CO transitions indicates the presence of material with temperatures > or approximately 100 K. Monte Carlo calculations of the molecular excitation and line transfer show that the envelope model derived from the dust emission can successfully reproduce the observed line intensities. The depletion of CO in the cold gas is modest compared to values inferred in objects like NGC 1333 IRAS 4, suggesting that the phase of large depletions through the entire envelope is short lived and may be influenced by the local star formation density. Emission in high-excitation lines of CO and H2CO requires the presence of a small amount of approximately 100 K material, comprising less than 1% of the total envelope mass and probably associated with the outflow or the innermost region of the envelope. The derived molecular abundances in the warm (Tkin > 20 K) envelope are similar to those found toward other class 0 YSOs like IRAS 16293-2422, though some species appear enhanced toward SMM 1. Taken together, the presented observations and analysis provide the first comprehensive view of the physical and chemical structure of the envelopes of deeply embedded young stellar objects in a clustered environment on scales between 1000 and 10,000 AU.

Envelope structure on 700 AU scales and the molecular outflows of low-mass young stellar objects.

Aperture synthesis observations of HCO+ J = 1-0, 13CO 1-0, and C18O 1-0 obtained with the Owens Valley Millimeter Array are used to probe the small-scale (5" approximately 700 AU) structure of the molecular envelopes of a well-defined sample of nine embedded low-mass young stellar objects in Taurus. The interferometer results can be understood in terms of: (1) a core of radius approximately or less than 1000 AU surrounding the central star, possibly flattened and rotating; (2) condensations scattered throughout the envelope that may be left over from the inhomogeneous structure of the original cloud core or that may have grown during collapse; and (3) material within the outflow or along the walls of the outflow cavity. Masses of the central cores are 0.001-0.1 M (solar), and agree well with dust continuum measurements. Averaged over the central 20" (3000 AU) region, an HCO+ abundance of 4 x 10(-8) is inferred, with a spread of a factor of 3 between the different sources. Reanalysis of previously presented single-dish data yields an HCO+ abundance of (5.0 +/- 1.7) x 10(-9), which may indicate an average increase by a factor of a few on the smaller scales sampled by the interferometer. Part of this apparent abundance variation could be explained by contributions from extended cloud emission to the single-dish C18O lines, and uncertainties in the assumed excitation temperatures and opacities. The properties of the molecular envelopes and outflows are further investigated through single-dish observations of 12CO J = 6-5, 4-3, and 3-2, 13CO 6-5 and 3-2, and C18O 3-2 and 2-1, obtained with the James Clerk Maxwell and IRAM 30 m telescopes, along with the Caltech Submillimeter Observatory. Ratios of the mid-J CO lines are used to estimate the excitation temperature, with values of 25-80 K derived for the gas near line centre. The outflow wings show a similar range, although Tex is enhanced by a factor of 2-3 in at least two sources. In contrast to the well-studied L1551 IRS 5 outflow, which extends over 10' (0.4 pc), seven of the remaining eight sources are found to drive 12CO 3-2 outflows over < or = 1' (0.04 pc); only L1527 IRS has a well-developed outflow of some 3'(0.12 pc). Estimates are obtained for the outflow kinetic luminosity, Lkin, and the flow momentum rate, FCO, applying corrections for line opacity and source inclination. The flow force FCO correlates with the envelope mass and with the 2.7 mm flux of the circumstellar disk. Only a weak correlation is seen with Lbol, while none is found with the relative age of the object as measured by integral Tmb(HCO+ 3-2)dV/Lbol. These trends support the hypothesis that outflows are driven by accretion through a disk, with a global mass infall rate determined by the mass and density of the envelope. The association of compact HCO+ emission with the walls of the outflow cavities indicates that outflows in turn influence the appearance of the envelopes. It is not yet clear, however, whether they are actively involved in sweeping up envelope material, or merely provide a low-opacity pathway for heating radiation to reach into the envelope.

Simultaneous amplification of terahertz difference frequencies by an injection-seeded semiconductor laser amplifier at 850 nm.

Two-frequency operation of an 850 nm semiconductor optical amplifier was achieved by simultaneously injection seeding it with two diode lasers. The two frequencies could be independently amplified without strong interference when they were separated by more than 10 GHz, and the spectral purity was preserved by the amplification process. At frequency differences below 10 GHz, unbalanced two-frequency output was observed, which can be explained by a two-mode interaction driven by the refractive index modulation at the beat frequency. The laser system is suitable for the difference-frequency generation of coherent terahertz radiation in ultra-fast photoconductors or nonlinear optical media.

Detection of water ice on Nereid.

We report the detection of the 1.5 and 2.0 micrometers absorption bands of water ice in the near-infrared reflection spectrum of Neptune's distant irregular satellite Nereid. The spectrum and albedo of Nereid appear intermediate between those of the Uranian satellites Umbriel and Oberon, suggesting a surface composed of a combination of water ice frost and a dark and spectrally neutral material. In contrast, the surface of Nereid appears dissimilar to those of the outer solar system minor planets Chiron, Pholus, and 1997 CU26. The spectrum thus provides support for the hypothesis that Nereid is a regular satellite formed in a circumplanetary environment rather than a captured object.

Chemical evolution of star-forming regions.

Recent advances in the understanding of the chemical processes that occur during all stages of the formation of stars, from the collapse of molecular clouds to the assemblage of icy planetesimals in protoplanetary accretion disks, are reviewed. Observational studies of the circumstellar material within 100-10,000 AU of the young star with (sub)millimeter single-dish telescopes, millimeter interferometers, and ground-based as well as space-borne infrared observatories have only become possible within the past few years. Results are compared with detailed chemical models that emphasize the coupling of gas-phase and grain-surface chemistry. Molecules that are particularly sensitive to different routes of formation and that may be useful in distinguishing between a variety of environments and histories are outlined. In the cold, low-density prestellar cores, radicals and long unsaturated carbon chains are enhanced. During the cold collapse phase, most species freeze out onto the grains in the high-density inner region. Once young stars ignite, their surroundings are heated through radiation and/or shocks, whereupon new chemical characteristics appear. Evaporation of ices drives a ''hot core'' chemistry rich in organic molecules, whereas shocks propagating through the dense envelope release both refractory and volatile grain material, resulting in prominent SiO, OH, and H2O emission. The role of future instrumentation in further developing these chemical and temporal diagnostics is discussed.

Simple, high-performance type II ?-BaB 2 O 4 optical parametric oscillator.

A visible /near-IR optical parametric oscillator (OPO) based on type II phase matching in ?-BaB2 O4 (BBO) is described. Pumped at 355 nm, this OPO covers 410 -2500 nm completely with a single set of standard Nd:YAG cavity optics. The output efficiency is >25 %, the linewidth of the OPO is narrower than 1 -2 cm-1 without the use of gratings or etalons, and the signal-beam divergence is <400 ?rad. Three type I BBO doubling crystals are used to extend the tuning range from 208 to 415 nm. Doubling efficiencies as high as 40 % are easily obtained. The reasons for the high doubling and overall system efficiency are discussed.

A line survey of Orion KL from 325 to 360 GHz.

We present a high-sensitivity spectral line survey of the high-mass star-forming region Orion KL in the 325-360 GHz frequency band. The survey was conducted at the Caltech Submillimeter Observatory on Mauna Kea, Hawaii. The sensitivity achieved is typically 0.1-0.5 K and is limited mostly by the sideband separation method utilized. We find 717 resolvable features consisting of 1004 lines, among which 60 are unidentified. The identified lines are due to 34 species and various isotopomers. Most of the unidentified lines are weak, and many of them most likely due to isotopomers or vibrationally or torsionally excited states of known species with unknown line frequencies, but a few reach the 2-5 K level. No new species have been identified, but we were able to strengthen evidence for the identification of ethanol in Orion and found the first nitrogen sulfide line in this source. The molecule dominating the integrated line emission is S02, which emits twice the intensity of CO, followed by SO, which is only slightly stronger than CO. In contrast, the largest number of lines is emitted from heavy organic rotors like HCOOCH3, CH3CH2CN, and CH3OCH3, but their contribution to the total flux is unimportant. CH3OH is also very prominent, both in the number of lines and in integrated flux. An interesting detail of this survey is the first detection of vibrationally excited HCN in the v2 = 2 state, 2000 K above ground. Clearly this is a glimpse into the very inner part of the Orion hot core.

HCl absorption toward Sagittarius B2.

We have detected the 626 GHz J = 1 --> 0 transition of hydrogen chloride (H35Cl) in absorption against the dust continuum emission of the molecular cloud Sagittarius B2. The observed line shape is consistent with the blending of the three hyperfine components of this transition by the velocity profile of Sgr B2 observed in other species. The apparent optical depth of the line is tau approximately 1, and the minimum HCl column density is 1.6 x 10(14) cm-2. A detailed radiative transfer model was constructed which includes collisional and radiative excitation, absorption and emission by dust, and the radial variation of temperature and density. Good agreement between the model and the data is obtained for HCl/H2 approximately 1.1 x 10(-9). Comparison of this result to chemical models indicates that the depletion factor of gas-phase chlorine is between 50-180 in the molecular envelope surrounding the SgrB2(N) and (M) dust cores.

A molecular line study of NGC 1333/IRAS 4.

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 outflow 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 even for very conservative mass estimates from the measured millimeter and submillimeter dust continuum. However, abundances scaled with respect to CO are similar to other dark molecular cloud cores. Such depletions could be mimicked by high dust optical depths or increased grain emissivities at the observing frequencies of 230 and 345 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 the 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 the outflowing gas is often both kinematically and spatially 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.

Chemical evolution of circumstellar matter around young stellar objects.

Recent observational studies of the chemical composition of circumstellar matter around both high- and low-mass young stellar objects are reviewed. The molecular abundances are found to be a strong function of evolutionary state, but not of system mass or luminosity. The data are discussed with reference to recent theoretical models.

Observations of chemical processing in the circumstellar environment.

High resolution interferometer and single-dish observations of young, deeply embedded stellar systems reveal a complex chemistry in the circumstellar environments of low to intermediate mass stars. Depletions of gas-phase molecules, grain mantle evaporation, and shock interactions actively drive chemical processes in different regions around young stars. We present results for two systems, IRAS 05338-0624 and NCG 1333 IRAS 4, to illustrate the behavior found and to examine the physical processes at work.