Calculations concerning interstellar isomeric abundance ratios for C3H and C3H2

The syntheses of interstellar c-C3H2, H2CCC, c-C3H, and HCCC, where "c" stands for the cyclic isomer, are thought to proceed via dissociative recombination of the precursor ions c-C3H3+ and H2CCCH+, which are themselves produced mainly via the radiative association reaction between C3H+ and H2. We have utilized ab initio methods to study the potential energy surface (PES) for the association of the linear ion C3H+ and H2 to form the isomers c-C3H3+ and H2CCCH+. The overall rate coefficient for radiative association has been calculated as a function of temperature via the phase space method. Our ab initio calculations show that the H2CCCH+ isomer is formed directly without an activation barrier from reactants, and that isomerization between the two isomers can occur readily via a low-energy pathway consisting of two transition states (saddle points on the PES) and one intermediate (local minimum on the PES). Calculations of the equilibrium coefficient for the isomerization H2CCCH+ <-> c-C3H3+ as a function of energy shows that equal abundances of these two ions should be produced as relaxation proceeds, in agreement with experimental measurements at high pressure. Our results confirm the important point that a simple ion-molecule association reaction can produce a cyclic hydrocarbon. If dissociative recombination reactions involving c-C3H3+ and H2CCCH+ maintain the carbon skeletal structure of the ions and produce roughly similar C3H/C3H2 branching ratios, then abundance ratios of unity are produced between the cyclic and noncyclic isomers of C3H and C3H2 via this mechanism. The large abundance ratio of c-C3H2 to H2CCC observed in TMC-1 can then be explained by differential destruction rates.     

Ion-molecule calculation of the abundance ratio of CCD to CCH in dense interstellar clouds

Laboratory measurements and calculations have been performed to determine the abundance ratio of the deuterated ethynyl radical (CCD) to the normal radical (CCH) which can be achieved in dense interstellar clouds via isotopic fractionation in the C2H2+ (HD) = C2HD+ (H2) system of reactions. According to this limited treatment, the CCD/CCH abundance ratio which can be attained is in the range 0.02-0.03 for the Orion molecular cloud and 0.01-0.02 for TMC-1. These ranges of numbers are in reasonable agreement with the observed values in Orion and TMC-1. However, the analysis of the CCD/CCH abundance ratio is complicated via the presence of competing fractionation mechanisms, especially in the low-temperature source TMC-1.     

Products of meteoric metal ion chemistry within planetary atmospheres. 1. Mg at Titan

We report results of quantum chemical calculations of Mg⁺/ligand bond dissociation energies involving ligands identified as major constituents of Titan's upper atmosphere. Trends identified in these results allow elucidation of the important bimolecular and termolecular reactions of Mg⁺, and of simple molecular ions containing Mg⁺, arising from meteoric infall into Titan's atmosphere. Our study highlights, and includes calculated rate coefficients for, crucial ligand-switching and ligand-stripping reactions which ensure that a dynamic equilibrium exists between atomic and molecular ions of Mg⁺. Neutralization of ionized meteoric Mg is expected to produce the radical MgNC in high yield. The highly polar MgNC radical should provide an excellent nucleation site for condensation of polar (e.g., HCN, CH₃CN, and HC₃N) and highly unsaturated (e.g., C₂H₂, C₄H₂, and C₂N₂) neutrals at comparatively high altitude, leading to precipitation of Mg-doped tholin-like material. The implications for Titan's prebiotic chemical evolution, of the surface deposition of such material (which may feasibly contain magnesium porphyrins, or other bioactive Mg-containing complexes) remain to be assessed.     

A quantum chemical study on the formation of ethanimine (CH<Subscript>3</Subscript>CHNH) in the interstellar ice

Ethanimine (CH₃CHNH) is an important prebiotic molecule since it is a precursor of amino acid \(\alpha \)-alanine in Strecker synthesis. Two isomers (E and Z) of ethanimine were detected in the molecular cloud Sagittarius B2 north during GBT-PRIMOS survey. A possible radical-molecule reaction pathway has been proposed for the formation of ethanimine in the interstellar medium (ISM) from some previously detected interstellar molecules like methylene (both triplet CH₂ (³B₁) and singlet CH₂ (¹A₁)) and methyenimine (CH₂NH). The mechanism has been studied in the gas phase and in water ice with the help of density functional theory at B2PLYPD/6-311++G (2d, p) level of theory. It is observed that E-ethanimine forms efficiently in gas phase but ice reactions are favorable only in the hot core of molecular clouds. Same is true for the formation of Z-ethanimine which forms only at the surface of water cluster as the height of entrance barrier for formation of Z-ethanimine is similar to that of E-ethanimine. Isomerization from E to Z form is also studied and found to be forbidden due to large entrance barrier. Out of the two reaction system CH₂ (³B₁) + CH₂NH and CH₂ (¹A₁) + CH₂NH, later is more favorable then the former one due to the small entrance barrier. Still, much of the detected abundance of ethanimine comes from the reaction of CH₂ (³B₁) with CH₂NH as since CH₂ (¹A₁) has very low abundance compared to the CH₂ (³B₁) in ISM. The proposed pathway seems to be a promising candidate for the ethanimine formation in ISM.     

A refractory Ca-SiO-H2-O2 vapor condensation experiment with implications for calciosilica dust transforming to silicate and carbonate minerals

Condensates produced in a laboratory condensation experiment of a refractory Ca-SiO-H₂-O₂ vapor define four specific and predictable deep metastable eutectic calciosilica compositions. The condensed nanograins are amorphous solids, including those with the stoichiometric CaSiO₃ pyroxene composition. In evolving dust-condensing astronomical environments they will be highly suitable precursors for thermally supported, dust-aging reactions whereby the condensates form more complex refractory silicates, e.g., diopside and wollastonite, and calcite and dolomite carbonates. This kinetically controlled condensation experiment shows how the aging of amorphous refractory condensates could produce the same minerals that are thought to require high-temperature equilibrium condensation. We submit that evidence for this thermal annealing of dust will be the astronomical detection of silica (amorphous or crystalline) that is the common, predicted, by-product of most of these reactions.     

Matrix isolation spectroscopy study of iron reactivity towards PAHs

The hypothesis of organometallic chemistry between polycyclic aromatic hydrocarbons (PAHs) and metals in the interstellar medium (ISM) has been recently proposed to contribute both to the unidentified interstellar infrared (UIR) emission and to the depletion of transition metals in the ISM. Since temperature and pressure conditions of the ISM can be easily simulated by matrix isolation techniques, we have undertaken the preparation of such species through cocondensation reactions of metal atoms (iron) with some PAHs (pyrene, coronene) in low temperature argon and dinitrogen matrices. The identification of species is achieved by means of FTIR and UV-visible spectroscopies. First results show that a weak reactivity occurs between neutral species at lOK: π-complexes, hydrogen-bonded compounds, and one hydride species have been observed.     

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

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

Edison — the international infrared space observatory

Edison is planned as a 1.7m telescope to be deployed at L2, and cooled non-cryogenically so that its lifetime would be from a minimum 3 years to possibly in excess of 10 years. Scientific projects have been proposed by 87 scientists from 11 countries. Due to its planned sensitivity and long lifetime it would be an excellent telescope to do comprehensive targeted searches for many different types of astronomical phenomena.     

Shock instabilities

It is well known that adiabatic shocks in ordinary gases are stable to both tranverse and longitudinal perturbations, but this need not be true if there are significant thermal effects due to chemical reactions or cooling processes. For example, detonation waves in gases are observed to form cellular structures if the chemical reaction is sufficiently temperature sensitive and a similar instability occurs in radiative shocks in the ISM if their speed exceeds 150 km s^–1. This means that interstellar shocks will be subject to this radiative instability in many cases. The temperature sensitivity of the nuclear reactions in Type I supernovae is also such that we would expect detonation waves in these objects to have a cellular structure.     

Coupled-channel calculation for cross section of fusion and barrier distribution of ${}^{16,17,18}\mbox{O} + {}^{16}\mbox{O}$ reactions

In this work, the effect of multi-phonon excitation on heavy-ion fusion reactions has been studied and fusion barrier distributions of energy intervals near and below the Coulomb barrier have been studied for ^16,17,18O + ¹⁶O reactions. The structure and deformation of nuclear projectiles have been studied. Given the adaptation of computations to experimental data, our calculations predict the behavior of reactions in intervals of energy in which experimental measurements are not available. In addition the S-factor for these reactions has been calculated. The results showed that the structure and deformation of a nuclear projectile are important factors. The S-factor, obtained in the coupled-channel calculations for the \({}^{16}\mbox{O} + {}^{16}\mbox{O}\), \({}^{17}\mbox{O} +{}^{16}\mbox{O}\) and \({}^{18}\mbox{O} +{}^{16}\mbox{O}\) reactions, showed good agreement with the experimental data and had a maximum value at an energy near 5, 4.5 and 4 MeV, respectively.     

Spatial pattern formation of interstellar medium

Population dynamics of multi-phased interstellar medium (ISM) is investigated by using the lattice model in position-fixed reaction. Interactions between three distinct phases of gas, cold clouds, warm gas, and hot gas give rise to cyclic phase changes in ISM. Such local phase changes are propagated in space, and stochastic steady-state spatial pattern is finally achieved. We obtain the following two characteristic patterns:

1. When the sweeping rate of a warm gas into a cold component is relatively high, cold clouds associated with warm gas form small-scale clumps and are dispersively distributed, whereas hot gas covers large fraction of space.
2. When the sweeping rate is relatively low, in contrast, warm gas and cold clouds are diffusively and equally distributed, while hot gas component is substantially localized.

     

Silica grain catalysis of methanol formation

The specific catalytic effect of a silica grain on the formation of methanol via the sequential addition of H atoms to CO adsorbed on the surface is investigated. A negatively charged defect on a siliceous edingtonite surface is found to reduce the gas phase barriers for the H + CO_ads and H + H₂C=O_ads reactions by 770 and 399 K, respectively, when compared to the same reactions in the gas phase. The catalytic effect of negatively charged surface sites could also be applicable to the hydrogenation of other adsorbed unsaturated species. However, the activation energies on the surface defect are still too large (1150 and 2230 K) for CH₃OH to form efficiently at 10–20 K in the interstellar medium via a classical mechanism. It is therefore suggested that quantum mechanical tunnelling through the activation barrier is required for these hydrogen addition reactions to proceed at such temperatures. The calculations show that because the adsorption energies of CO and H₂C=O on the negatively charged defect are substantial, CH₃OH may form efficiently during the warm-up period in star-forming regions.     

Optimal searches for asteroids

Optimal searches for a fixed object are discussed and the rigorous analytical results of discrete search theory are presented. They show that the totally optimal, the uniformly optimal, the locally optimal, and the fastest searches are identical under not too restrictive assumptions. The Mathematical formalism is illustrated by an Earth-approaching asteroid search and optimal searches for such objects are explicitly constructed. The approximation that Earth-approaching asteroids are fixed is equivalent to having a very high $\text{(}\text{1}\text{?}\text{00}\text{square degrees/hr)}$ search rate. Generalizations to other types of astronomical search are briefly mentioned.     

Comet Grains: Their IR Emission and Their Relation to ISm Grains

Comets and the chondritic porous interplanetary dust particles (CP IDPs) that they shed in their comae are reservoirs of primitive solar nebula materials. The high porosity and fragility of cometary grains and CP IDPs, and anomalously high deuterium contents of highly fragile, pyroxene-rich Cluster IDPs imply these aggregate particles contain significant abundances of grains from the interstellar medium (ISM). IR spectra of comets (3–40 μm) reveal the presence of a warm (near-IR) featureless emission modeled by amorphous carbon grains. Broad andnarrow resonances near 10 and 20 microns are modeled by warm chondritic (50% Feand 50% Mg) amorphous silicates and cooler Mg-rich crystalline silicate minerals, respectively. Cometary amorphous silicates resonances are well matched by IRspectra of CP IDPs dominated by GEMS (0.1 μm silicate spherules) that are thought to be the interstellar Fe-bearing amorphous silicates produced in AGB stars. Acid-etched ultramicrotomed CP IDP samples, however, show that both the carbon phase (amorphous and aliphatic) and the Mg-rich amorphous silicate phase in GEMS are not optically absorbing. Rather, it is Fe and FeS nanoparticles embedded in the GEMS that makes the CP IDPs dark. Therefore, CP IDPs suggest significant processing has occurred in the ISM. ISM processing probably includes in He⁺ ion bombardment in supernovae shocks. Laboratory experiments show He⁺ ion bombardment amorphizes crystalline silicates, increases porosity, and reduces Fe into nanoparticles. Cometary crystalline silicate resonances are well matched by IR spectra of laboratory submicron Mg-rich olivine crystals and pyroxene crystals. Discovery of a Mg-pure olivine crystal in a Cluster IDP with isotopically anomalous oxygen indicates that a small fraction of crystalline silicates may have survived their journey from AGB stars through the ISM to the early solar nebula. The ISM does not have enough crystalline silicates (<5%), however, to account for the deduced abundance of crystalline silicates in comet dust. An insufficient source of ISMMg-rich crystals leads to the inference that most Mg-rich crystals in comets are primitive grains processed in the early solar nebula prior to their incorporation into comets. Mg-rich crystals may condense in the hot (～1450 K), inner zones of the early solar nebula and then travel large radial distances out to the comet-forming zone. On the other hand, Mg-rich silicate crystals may be ISM amorphous silicates annealed at ～1000 K and radially distributed out to the comet-forming zone or annealed in nebular shocks at ～5-10 AU. Determining the relative abundance of amorphous and crystalline silicatesin comets probes the relative contributions of ISM grains and primitive grains to small, icy bodies in the solar system. The life cycle of dust from its stardust origins through the ISM to its incorporation into comets is discussed.     

The evolution of superbubbles and the detection of Lyα in star-forming galaxies

The detection of Ly α emission in star-forming galaxies in different shapes and intensities (always smaller than predicted for case B recombination) has puzzled the astronomical community for more than a decade. Here we use two-dimensional calculations to follow the evolution of superbubbles and of the H  ii regions generated by the output of UV photons from massive stars. We show the impact caused by massive star formation in the ISM of different galaxies and we look at the conditions required to detect Ly α emission from a nuclear H  ii region, and the variety of profiles that may be expected as a function of time.     

Interstellar cyanomethane

We have made an observational study of the newly identified cyanomethane radical CH2CN and the possibly related species CH3CN with the goals of (1) elucidating the possible role of reactions of the type CnHm(+) + N in astrochemistry, and (2) providing a possible test of Bates's models of dissociative electron recombination. We find a remarkably different abundance ratio CH2CN/CH3CN in TMC-1 and Sgr B2, which we deduce is a result of the large difference in temperature of these objects. Studies of CH2CN and CH3CN in other sources, including two new detections of CH2CN, support this conclusion and are consistent with a monotonic increase in the CH2CN/CH3CN ratio with decreasing temperature over the range 10-120 K. This behavior may be explained by the destruction of CH2CN by reaction with O. If this reaction does not proceed, then CH2CN and CH3CN are concluded to form via different chemical pathways. Thus, they do not provide a test of Bates's conjectures (they do not both form from CH3CNH+). CH2CN is then likely to form via C2H4(+) + N --> CH2CNH+, thus demonstrating the viability of this important reaction in astrochemistry. The T dependence of the CH2CN/CH3CN ratio would then reflect the increasing rate of the C2H4(+) + N reaction with decreasing temperature.     

Olivine zoning and retrograde olivine‐orthopyroxene‐metal equilibration in H5 and H6 chondrites

Abstract— Electron microprobe studies of several H5 and H6 chondrites reveal that olivine crystals exhibit systematic Fe‐Mg zoning near olivine‐metal interfaces. Olivine Fa concentrations decrease by up to 2 mol% toward zoned taenite + kamacite particles (formed after relatively small amounts of taenite undercooling) and increase by up to 2 mol% toward zoneless plessite particles (formed after ?200 °C of taenite undercooling). The olivine zoning can be understood in terms of localized olivine‐orthopyroxene‐metal reactions during cooling from the peak metamorphic temperature. The silicate‐metal reactions were influenced by solid‐state metal phase transformations, and the two types of olivine zoning profiles resulted from variable amounts of taenite undercooling at temperatures <700 °C. The relevant silicate‐metal reactions are modeled using chemical thermodynamics. Systematic olivine Fe‐Mg zoning adjacent to metal is an expected consequence of retrograde silicate‐metal reactions, and the presence of such zoning provides strong evidence that the silicate and metallic minerals evolved in situ during cooling from the peak metamorphic temperature.     

Astronomical identification of the C3H radical

The C3H radical, a linear carbon chain with a 2 pi electronic ground state, has been identified in the millimeter-wave spectra of two astronomical sources, IRC +10216 and TMC-1, and conclusively confirmed (accompanying Letter) in a laboratory glow discharge. In IRC +10216 four rotational transitions have been observed, three in the lower fine-structure ladder (2 pi 1/2) and one in the upper (2 pi 3/2), each a resolved or partially resolved lambda-doublet. In TMC-1, both lambda components of the lowest lying 3/2 --> 1/2 transition of the 2 pi 1/2 ladder have been observed, each with well-resolved hfs. In IRC +10216 the excitation of C3H is similar to that of SiCC: the rotational temperature Trot within the 2 pi 1/2 ladder is low (8.5 K), owing to rapid radiative decay, while Trot across the ladders is high (approximately 52 K) because interconnecting far-IR radiative transitions are only weakly permitted. The column density of C3H in IRC +10216 averaged over the estimated source diameter of 84" is 2.8 x 10(13) cm-2, an order of magnitude less than that of C2H and C4H. A determination of the spectroscopic constraints of C3H that permitted the entire radio spectrum of this molecule to be calculated to high accuracy has been derived from analysis of the combined astronomical and laboratory data presented in the accompanying Letter.     

FTIR 2–16 micron spectroscopy of micron‐sized olivines from primitive meteorites

Abstract— Infrared spectra of mineral grains from primitive meteorites could be useful for comparison with astronomical infrared spectra since some of their grains might be similar to those formed in the planet‐forming disks around young stars or in the envelopes surrounding late‐type stars. To assess the usefulness of meteorite spectra, olivine grains separated from primitive meteorites have been analyzed using FTIR microscope techniques in the 2–16 μm wavelength range. The sub‐micron sizes of the grains made a complex preparation process necessary. Five characteristic bands were measured near 11.9, 11.2, 10.4, 10.1, and 10.0 μm. The results of 59 analyses allow the calculation of band positions for meteoritic olivines as a function of their iron and magnesium contents. Comparison of the meteoritic results with astronomical data for comets and dust around young and old stars, which exhibit bands similar to the strongest infrared bands observed in the grains (at 11.2 μm), show that the spectral resolution of the astronomical observations is too low to ascertain the exact iron and magnesium (Mg: Fe) ratio of the dust in the 8–13 μm wavelength range.     

The Stokes phase portraits of descattered pulse profiles of a few pulsars

The observing signals from pulsar are always influenced by the interstellar medium (ISM) scattering. In the lower frequency observation, the intensity profiles are broadened and the plane of polarization angle (PPA) curves are flattened by the scattering effect of the ISM. So before we analyze the scattered signal, we should take a proper approach to clear scattering effect from it. Observing data and simulation have shown that the Stokes phase portraits I–U, I–Q and Q–U are also distorted by the ISM scattering. In this paper, a simulation is held to demonstrate a scattering and a descattering of the Stokes phase portraits of a single pulse profile of a pulsar. As a realization of the simulation method, this paper has studied the descattering of Stokes phase portraits of lower frequency observation of PSR B1356?60, PSR B1831?03, PSR B1859+03, PSR B1946+35.