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Huntress, W. T., Jr.

Publications and source records attributed to Huntress, W. T., Jr..

At least 19 records

Modeling the chemistry of the dense interstellar clouds. I - Observational constraints for the chemistry

A search for correlations arising from molecular line data is made in order to place constraints on the chemical models of interstellar clouds. At 10 to the 21st H2/sq cm, N(CO) for dark clouds is a factor of six greater than the value for diffuse clouds. This implies that the strength of the UV radiation field where CO shields itself from dissociation is about one-half the strength of the average Galactic field. The dark cloud data indicate that the abundance of CO continues to increase with A(V) for directions with A(V) of 4 mag or less, although less steeply with N(H2) than for diffuse clouds. For H2CO, a quadratic relationship is obtained in plots versus H2 column density. The data suggest a possible turnover at the highest values for A(V). NH3 shows no correlation with H2, C(O-18), HC3N, or HC5N; a strong correlation is found between HC5N and HC3N, indicating a chemical link between the cyanopolyynes.

Federman, S. R.

Diffuse interstellar clouds as a chemical laboratory - The chemistry of diatomic carbon species

The chemistry of C2, CH, and CO in diffuse interstellar clouds is analyzed and compared to absorption line measurements toward background stars. Analytical expressions in terms of column densities are derived for the rate equations. The results indicate that in clouds with 4 mag of visual extinction, the abundance of C+ has to decrease by a factor of about 15 from the value traditionally used for clouds with 1 mag of extinction. The rate coefficients for the reactions C+ + CH - C2+ + H and C+ + H2 - CH2+ + h-nu need to be reduced from previous estimates. Chemical arguments are presented for the revised rate coefficients.

Federman, S. R.

A survey of bimolecular ion-molecule reactions for use in modeling the chemistry of planetary atmospheres, cometary comae, and interstellar clouds

All bimolecular positive ion-molecule reactions reported from 1965 to 1985 for temperatures below 1000 K are included in the present survey of those ion-molecule reactions pertinent to the chemistries of planetary atmospheres, cometary comae, and interstellar clouds. This survey is intended as an update of the first, by Huntress (1977). The tabular presentation is organized according to reactant ion, with cross-references for both the ionic and the neutral reactants as well as the ionic and neutral products.

Anicich, V. G.

Chemistry of chlorine in dense interstellar clouds

Laboratory experiments and theoretical modeling show that the chemistry of chlorine is fairly simple in dense interstellar clouds, with Cl and HCl as the only species whose fractional abundances are significant. The estimated fraction of gas-phase chlorine present as HCl lies between 25-65 percent, in good agreement with the recent observations of the ground state HCl transition by Blake, Keene, and Philips (1985). These results, combined with the observational limits on HCl, indicate that chlorine is not severely depleted in dense interstellar clouds.

Blake, G. A.

Ion-molecule reactions of hydrocarbon ions in C2H2 and HCN

Rate coefficients and product distributions have been determined for reaction of the ions C(x)H(y)+ (x ranging from 1 to 4, and y ranging from 0 to 4) with C2H2 and HCN. The measurements were obtained using the ion cyclotron resonance technique at 298 K. In several reactions an association product was observed at pressures as low as 0.000001 torr, and in these cases stabilization of the intermediate was assumed to be by photon emission. Most of the reaction studied yield ions having a larger carbon skeleton than the reactant ion. These reactions provide routes for building large organic and organonitrogen molecules in combustion zones of unsaturated hydrocarbon flames and in astrochemical environments.

Anicich, V. G.

Chemistry in dynamically evolving clouds

A unified model of chemical and dynamical evolution of isolated, initially diffuse and quiescent interstellar clouds is presented. The model uses a semiempirically derived dependence of the observed cloud temperatures on the visual extinction and density. Even low-mass, low-density, diffuse clouds can collapse in this model, because the inward pressure gradient force assists gravitational contraction. In contrast, previous isothermal collapse models required the low-mass diffuse clouds to be unrealistically cold before gravitational contraction could start. Theoretically predicted dependences of the column densities of various atoms and molecules, such as C and CO, on visual extinction in diffuse clouds are in accord with observations. Similarly, the predicted dependences of the fractional abundances of various chemical species (e.g., CO, H2CO, HCN, HCO(+)) on the total hydrogen density in the core of the dense clouds also agree with observations reported to date in the literature. Compared with previous models of interstellar chemistry, the present model has the potential to explain the wide spectrum of chemical and physical properties of both diffuse and dense clouds with a common formalism employing only a few simple initial conditions.

Tarafdar, S. P.

The chemistry of phosphorus in dense interstellar clouds

Laboratory experiments show that the ion-molecule chemistry of phosphorus is significantly different from that of nitrogen in dense interstellar clouds. The PH3 molecule is not readily formed by gas-phase, ion-molecule reactions in these regions. Laboratory results used in a simple kinetic model indicate that the most abundant molecule containing phosphorus in dense clouds is PO.

Thorne, L. R.

Ion-molecule reactions in unsaturated hydrocarbons - Allene, propyne, diacetylene, and vinylacetylene

Ion-molecule reactions in allene, propyne, diacetylene, and vinylacetylene (1-buten-3-yne) have been studied at near-thermal energies by the technique of ion cyclotron resonance mass spectrometry. Rate coefficients and branching ratios are reported for the reactions of C3Hn(+) (n = 1-4) with allene and propyne and for the reactions of C4Hn(+) (n = 0-5) with diacetylene and vinylacetylene. Branching ratios are also given for the reactions of C4Hn(+), C5Hn and C6Hn(+) with propyne and for reactions of C6Hn(+) with diacetylene and vinylacetylene. More than 90 percent of the reactive channels lead to product ions having a larger carbon skeleton than the reactant ion. Evidence for ions with the same m/e ratio having differing reactivities was obtained for C3Hn(+), C6H7(+), and C7H7(+). Ion reaction sequences in allene and propyne were followed at higher pressures (0.0001 torr) to investigate secondary, tertiary, and higher order processes.

Anicich, V. G.

Dependence of interstellar depletion on hydrogen column density - Possibilities and implications

A reexamination of the observed column densities of various elements in diffuse clouds suggests that almost all elements including oxygen, nitrogen, sulfur, and argon may be depleted with respect to hydrogen in interstellar clouds with large hydrogen column density. The amount of depletion varies from element to element and increases with increasing column density of hydrogen nuclei. This result is in qualitative agreement with the depletion of oxygen and sulfur independently inferred from the gas phase chemistry of sulfur in dense clouds. The rate of increase of depletion with hydrogen column density implied by the present study is large. It is possible that observational selection effects may have amplified the real dependence on N(H). A broad spectrum of C/O ratios ranging from values greater than unity to values less than unity appears possible for interstellar clouds, which would have the effect of a large variation in chemical composition from cloud to cloud.

Tarafdar, S. P.

Loss of CO/+/ ions by reaction with H2 in OMC-1

The temperature dependence of the rate constant for the reaction CO(+)+H2 yields HCO(+) has been measured in the temperature range 100-390 K. The rate constant has no dependence on temperature in this range, indicating that at the temperatures prevalent in OMC-1, the rate of loss of CO(+) by reaction with H2 is much too large to allow for the observed column abundance under steady-state conditions.

Huntress, W. T., Jr.

Sulfur chemistry in dense interstellar clouds

A model is presented for the gas phase chemistry of molecules containing sulfur in dense interstellar clouds. The sulfur chemistry is different from that used in previous models as a result of an extensive search of the recent literature and the availability of new laboratory data. The changes have a significant effect on the calculated abundance of sulfur compounds. The linked chemistry of sulfur and oxygen in the present model requires a severe depletion of sulfur and low fractional abundances of both O and O2 in the dense clouds. In contrast, the high abundance of SO and the low abundance of CS relative to SO in the HVS in the KL may indicate an oxygen-rich, high temperature environment compared to OMC-1. The formation of S-H bonds is slow because of the absence of radiative association between S(+) and H2. The present model underestimates the abundance of H2S unless a radiative association reaction between HS(+) and H2 is postulated.

Prasad, S. S.

Temperature dependence of the hydrogen atom abstraction reactions of Cl/+/ and HCl/+/ with H2

Rate constants are reported for the reactions of Cl(+) and HCl(+) with H2 over the temperature range 150-400 K. The Cl(+) reaction has a positive temperature dependence that follows the Arrhenius form k1 = A exp(-169/T). The reaction of HCl(+) has a negative temperature dependence that follows the form k2 = AT to the -0.6 power. The implication of these results for interstellar chemistry is commented on. Schematic potential surfaces for the reactions are suggested.

Cates, R. D.

An ICR investigation of ion-molecule reactions of HCN

Laboratory reaction rates and product distributions measured by the ion cyclotron resonance technique are reported for a series of reactions of HCN(+) ions with the neutral molecules HCN, CH4, NH3, H2O, CO, CO2, N2 and O2. Rate coefficients are also reported for reactions of positive ions derived from these molecules with HCN. A comparison of the results with a survey of literature values for rate coefficients of HCN(+) reactions shows some exothermic proton transfers from HCN(+) to be inefficient.

Mcewan, M. J.

Laboratory studies of some of the major ion-molecule reactions occurring in cometary comae

Laboratory results have been obtained for some of the key ion-molecule reactions which should occur in the inner coma of comets. A complete listing is given of laboratory data presently available for ion-molecule reactions occurring in a mixture of H2O, CO2, CO, CH4, N2, and NH3 cometary volatiles. From these data, the most important reactions occurring in the coma of a water-dominated comet are extracted for use in models of the physics and chemistry of cometary comae.

Huntress, W. T., Jr.

A model for gas phase chemistry in interstellar clouds. II - Nonequilibrium effects and effects of temperature and activation energies

The chemical evolution of diffuse and dense interstellar clouds is examined via the time-dependent model outlined by Prasad and Huntress (1980). This paper presents specific results for CH, CO, CH4, O2, CH2O, CN, C2, C2H, HC3N, and NH3. Comparison with observations and predictions of other contemporary models show that cloud temperature plays a very important role through the inverse temperature dependence of radiative association reactions and through activation energies in neutral reactions and selected ion-molecule reactions. The observed fractional abundance of CN with respect to H2 and more accurate recent laboratory data on CN + O and CN + O2 reactions suggest that there is an unidentified, yet efficient, mechanism for conversion of O and O2 into polyatomic species. C2H and HC3N are synthesized early in the history of dense clouds. The value of the fractional abundance of C2H remains high, because as the cloud cools down the activation energy in the C2H + O reaction closes down this most important loss channel. A rapidly decreasing fractional abundance of O with time can also accomplish the same result. The value of the fractional abundance of HC3N remains high because it is an unreactive molecule and probably does not condense readily onto grains.

Prasad, S. S.

Miniature cyclotron resonance ion source using small permanent magnet

An ion source using the cyclotron resonance principle is described. A miniaturized ion source device is used in an air gap of a small permanent magnet with a substantially uniform field in the air gap of about 0.5 inch. The device and permanent magnet are placed in an enclosure which is maintained at a high vacuum (typically 10 to the minus 7th power) into which a sample gas can be introduced. The ion beam end of the device is placed very close to an aperture through which an ion beam can exit into the apparatus for an experiment.

Anicich, V. G.

Interstellar sulfur chemistry

The results of a chemical model of SO, CS, and OCS chemistry in dense clouds are summarized. The results are obtained from a theoretical study of sulfur chemistry in dense interstellar clouds using a large-scale time-dependent model of gas-phase chemistry. Among the results are the following: (1) owing to activation energy, the reaction of CS with O atoms is efficient as a loss mechanism of CS during the early phases of cloud evolution or in hot and oxygen-rich sources such as the KL nebula; (2) if sulfur is not abnormally depleted in dense clouds, then the observed abundances of SO, SO2, H2S, CS, OCS, H2CS, and SiS indicate that sulfur is mostly atomic in dense clouds; and (3) OCS is stable against reactions with neutral atoms and radicals in dense clouds.

Prasad, S. S.