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.

Molecular interactions and hydrogen bond tunneling dynamics: some new perspectives.

The recent development of tunable far-infrared lasers and other high-resolution spectroscopic probes of weakly bound clusters is having a significant impact on our understanding of intermolecular forces and on the complex quantum tunneling dynamics that occur in hydrogen-bonded systems. Far-infrared studies of a variety of interactions are discussed, including several prototypical water-hydrophobe complexes, the water trimer, and the ammonia dimer. Particular attention is paid to the inversion of spectroscopic data to yield detailed intermolecular potential energy surfaces. Investigations of nonpairwise additivity are also described.

Benzene forms hydrogen bonds with water.

Fully rotationally resolved spectra of three isotopic species of 1:1 clusters of benzene with water (H(2)O, D(2)O, and HDO) were fit to yield moments of inertia that demonstrate unambiguously that water is positioned above the benzene plane in nearly free internal rotation with both hydrogen atoms pointing toward the pi cloud. Ab initio calculations (MP2 level of electron correlation and 6-31 G(**) basis set with basis set superposition error corrections) predict a binding energy D(e) greater, similar 1.78 kilocalories per mole. In both the experimental and theoretical structures, water is situated nearly 1 angstrom within the van der Waals contacts of the monomers, a clear manifestation of hydrogen bond formation in this simple model of aqueous-pi electron interactions.

Exercise-induced hypertension in normotensive patients with NIDDM.

The aim of this study was to determine whether blood pressure during mild to moderate exercise is abnormal in patients with non-insulin-dependent diabetes mellitus (NIDDM). The study group consisted of 11 patients with NIDDM and 11 nondiabetic subjects of comparable age and body mass index. All subjects were sedentary and basally normotensive. Bicycle ergometry was used to assess the effect of exercise on blood pressure at a steady state of 70-75 W, with a target duration of 20 min. Blood pressure was measured basally and every 5 min. Greater exercise-induced systolic blood pressure (mean max 208.0 +/- 6.0 vs. 177.0 +/- 3.0 mmHg) occurred in the NIDDM group (P less than 0.001). Neither pulse rate nor diastolic blood pressure differed between the groups before or during exercise. Return to basal pulse and blood pressure was similar. Mild to moderate exercise induces greater systolic blood pressure in sedentary patients with NIDDM. Because exercise is recommended as one therapeutic modality, intraexercise blood pressure should be considered in assessing the safety of this form of treatment.

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.

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.

Pseudorotation in the D2O trimer.

Far-infrared spectra of Ar/D2O supersonic expansions have been recorded between 39 and 44 cm-1, in which a c-type band centered at 41.1 cm-1 was observed. This new band, attributed to the cyclic water trimer, has the same ground state rotational constants as the (D20)3 98 cm-1 a-type band reported by Liu et al. [J. Am. Chem. Soc. 116 (1994) 3507]. Fits of the observed far-infrared band positions to an effective one-dimensional potential require a substantially larger pseudorotation barrier or effective moment of inertia than predicted theoretically. Estimated frequencies of unobserved transitions in the pseudorotation manifolds of (D2O)3 and (H20)3 are presented as a guide to future experimental searches.

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).

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.

The molecular emission-line spectrum of IRC +10216 between 330 and 358 GHz.

We have conducted a spectral line survey of IRC +10216 using the Caltech Submillimeter Observatory to an average sensitivity of < or approximately 95 mK. A deconvolution algorithm has been used to derive the continuous single-sideband spectrum from 330.2 to 358.1 GHz. A total of 56 spectral lines were detected of which 54 have been identified with 8 molecules and a total of 18 isotopomers. The observed lines are used to derive column densities and relative abundances for the detected species. Within this frequency range the spectral lines detected contribute the majority of the total flux emitted by IRC +10216. We use the derived column densities and excitation temperatures to simulate the molecular line emission (assuming LTE) at frequencies up to 1000 GHz. The observed and simulated flux from line emission is compared to broadband total flux measurements and to dust emission assuming a power-law variation of the dust emissivity. We conclude that significant corrections for the line flux must be made to broadband flux measurements of IRC +10216 at wavelengths longer than approximately 750 micrometers.

The circumstellar environment of IRAS 05338-0624.

Millimeter continuum and spectral line observations with 10", 30", and 60" resolution are used to characterize the structure and chemistry of the gas around the young, embedded star, IRAS 05338-0624. On arcminute scales, emission from dense gas tracers outline an isolated condensation centered on the IRAS source position. The condensation is characterized by a size of approximately 60", a density of 2 x 10(5) cm-3, and a virial mass of 40 M solar. Interferometric CS J = 2-1 observations show two peaks, one toward the continuum peak and the other toward a position 14" west and 8" south. Single-dish maps of SO, CH3OH, and SiO show pronounced wing emission to the west of the IRAS source, which interferometer observations reveal to be a compact region of outflow activity. CS emission as redshifted and blueshifted velocities reveals a bipolar outflow oriented with a position angle of 45 degrees, while SiO emission appears to be tracing a fast shock interaction region at the CS red-lobe peak, 14" west and 8" south of the IRAS source. Finally, H13CO+ emission traces clumps of quiescent gas toward the IRAS source and adjacent to the blue lobe of the outflow. Column densities and molecular fractional abundances are derived to explore the interaction between the surrounding condensation and the young stellar object. We find evidence for gas phase depletions within the overall condensation in several gas tracers (CO, CS, HCN, SO) but not in the region immediately around the young stellar object. Enhanced abundances of SO, CH3OH, and SiO (by factors of 4, >100, >1000, respectively) are observed in the shocked gas; these enhancements may be explained in terms of a nondissociative shock liberating mantle materials that contain some amount of refractory materials, a moderate velocity dissociative shock in which only minor sputtering of Si occurs, or a shock that impacts surrounding material with a range of speeds.

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.

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.

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.