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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.  相似文献   
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On 15 August 1994 we launched the EUVS sounding rocket payload to observe the 825-1110 angstrom region of Venus's far ultraviolet airglow spectrum. The EUVS telescope/spectrograph obtained good data at five times higher spectral resolution than was previously available in the far ultraviolet. We present these data and compare our results to those obtained by the Galileo UVS and Venera 11/12 UV spectrophotometers. We identify several new spectral emission features, including both singly ionized nitrogen and molecular nitrogen in Venus's spectrum. We also see evidence for electron-impact-induced emission from CO. Finally, the EUVS data indicate that the "Ar" emissions detected in Venus's far ultraviolet spectrum by Venera 11/12 spectrophotometers are in fact not due to argon, thus eliminating the discrepancy between in situ and remote sensing measurements.  相似文献   
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Infrared spectra of Io in the region 2.5-5.0 micrometers, including new observational data, are analyzed using detailed laboratory studies of plausible surface ices. Besides the absorption bands attributable to sulfur dioxide frosts, four infrared spectral features of Io are shown to be unidentified. These unidentified features show spatial and temporal band strength variations. One pair is centered around 3.9 micrometers (3.85 and 3.91 micrometers) and the second pair is centered around 3.0 micrometers (2.97 and 3.15 micrometers). These absorptions fall close to the fundamental stretching modes in H2S and H2O, respectively. The infrared absorption spectra of an extensive set of laboratory ices ranging from pure materials, to binary mixtures of H2S and H2O (either mixed at different concentrations or layered), to H2O:H2S:SO2 mixtures are discussed. The effects of ultraviolet irradiation (120 and 160 nm) and temperature variation (from 9 to 130 K) on the infrared spectra of the ices are examined. This comparative study of Io reflectance spectra with the laboratory mixed ice transmission data shows the following: (1) Io's surface most likely contains H2S and H2O mixed with SO2. The 3.85- and 3.91-micrometers bands in the Io spectra can be accounted for by the absorption of the S-H stretching vibration (nu 1) in H2S clusters and isolated molecules in an SO2-dominated ice. The weak 2.97- and 3.15-micrometers bands which vary spatially and temporally in the Io spectra coincide with the nu 3 and nu 1 O-H stretching vibrations of clusters of H2O molecules complexed, through hydrogen bonding and charge transfer interactions, with SO2. (2) The observations are well matched qualitatively by the transmission spectra of SO2 ices containing about 3% H2S and 0.1% H2O which have been formed by the condensation of a mixture of the gases onto a 100 K surface. (3) No new features are produced in the region 2.5 to 5.0 micrometers in the spectrum of these ices under prolonged ultraviolet irradiation or temperature variation up to 120 K. (4) Comparison of the Io spectra to transmission spectra of both mixed molecular ices and layered ices indicates that only the former can explain the shifts and splitting of the absorption bands seen in the Io spectrum and additionally can account for the fact that solid H2S is observed in the surface material of Io at temperature and pressure conditions above the sublimation point of pure H2S.  相似文献   
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When Hurricane Iniki struck the Hawaiian Islands in September 1992, it provided a rare opportunity to examine the immediate effects of a hurricane on two intertidal benthic communities off the reefs of O'ahu, Hawai'i. The Niu Beach site contained large, obvious aggregations of the tube building polychaete Diopatra dexiognatha, and the Wailupe Beach site was without obvious tubiculous fauna at the surface. Ten replicate sediment cores were taken before and after the hurricane with a 7.6 cm PVC corer and organisms were identified to family and enumerated. There were no substantial depletions or loss of taxa after the hurricane. Oligochaetes were the most dominant taxa pre-and post-hurricane. The abundance of all dominant polychaete families increased post-hurricane. The three most abundant polychaetes were capitellids and D. dexiognatha (Onuphidae) at Niu Beach and Pygospio muscularis (Spionidae) at Wailupe Beach. We suggest that D. dexiognatha and P. muscularis help stabilize the sediments since they both form dense tube mats while capitellids and oligochaetes are considered highly adaptive surface burrowers that can take advantage of newly disturbed sediments. Overall, there was no substantial effect observed on the intertidal fauna exposed to this severe disturbance. It is suggested here that invertebrate communities in this area are adapted to survive and thrive in high-energy environments and possibly benefit from dense aggregations of tube building polychaetes.  相似文献   
58.
We present the 2320-2050 cm-1 (4.31-4.88 micrometers) infrared spectra of 16 solid-state nitriles, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C triple bond N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile (phenylcyanide), 9-anthracenecarbonitrile, dimethylcyanamide, isopropylnitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyruvonitrile, dicyandiamide, cyanamide, n-butylisocyanide, methylisocyanoacetate, diisopropylcarbodiimide, and hydrogen cyanide. The C triple bond N stretching bands of the majority of nitriles fall in the 2300-2200 cm-1 (4.35-4.55 micrometers) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contrast, the isonitriles and a few exceptional nitriles and related species produce bands at lower frequencies spanning the 2200-2080 cm-1 (4.55-4.81 micrometers) range. These features also have similar positions in both Ar and H2O matrices, and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C triple bond N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165 cm-1 (4.62 micrometers) "XCN" interstellar feature and the 4550 cm-1 (2.2 micrometers) feature of various objects in the solar system are discussed.  相似文献   
59.
We have discovered a new IR emission feature at 1905 cm-1 (5.25 microns) in the spectrum of BD +30 degrees 3639. This feature joins the family of well-known IR emission features at 3040, 2940, 1750, 1610, "1310," 1160, and 890 cm-1 (3.3, 3.4, 5.7, 6.2, "7.7," 8.6, and 11.2 microns). The origin of this new feature is discussed and it is assigned to an overtone or combination band involving C-H bending modes of polycyclic aromatic hydrocarbons (PAHs). Laboratory work suggests that spectral studies of the 2000-1650 cm-1 (5.0-6.1 microns) region may be very useful in elucidating the molecular structure of interstellar PAHs. The new feature, in conjunction with other recently discovered spectral structure, suggests that the narrow IR emission features originate in PAH molecules rather than large carbon grains. Larger species are likely to be the source of the broad underlying "plateaus" seen in many of the spectra.  相似文献   
60.
Mehl S  Hill MC  Leake SA 《Ground water》2006,44(6):792-796
Many ground water modeling efforts use a finite-difference method to solve the ground water flow equation, and many of these models require a relatively fine-grid discretization to accurately represent the selected process in limited areas of interest. Use of a fine grid over the entire domain can be computationally prohibitive; using a variably spaced grid can lead to cells with a large aspect ratio and refinement in areas where detail is not needed. One solution is to use local-grid refinement (LGR) whereby the grid is only refined in the area of interest. This work reviews some LGR methods and identifies advantages and drawbacks in test cases using MODFLOW-2000. The first test case is two dimensional and heterogeneous; the second is three dimensional and includes interaction with a meandering river. Results include simulations using a uniform fine grid, a variably spaced grid, a traditional method of LGR without feedback, and a new shared node method with feedback. Discrepancies from the solution obtained with the uniform fine grid are investigated. For the models tested, the traditional one-way coupled approaches produced discrepancies in head up to 6.8% and discrepancies in cell-to-cell fluxes up to 7.1%, while the new method has head and cell-to-cell flux discrepancies of 0.089% and 0.14%, respectively. Additional results highlight the accuracy, flexibility, and CPU time trade-off of these methods and demonstrate how the new method can be successfully implemented to model surface water-ground water interactions.  相似文献   
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