The physical and infrared spectral properties of CO2 in astrophysical ice analogs

Both laboratory measurements and theory indicate that CO2 should be a common component in interstellar ices. We show that the exact band position, width, and profile of the solid-state 12CO2 infrared bands near 3705, 3600, 2340, and 660 cm-1 (2.70, 2.78, 4.27, and 15.2 micrometers) and the 13CO2 band near 2280 cm-1 (4.39 micrometers) are dependent on the matrix in which the CO2 is frozen. Measurements of these bands in astronomical spectra can be used to determine column densities of solid-state CO2 and provide important information on the physical conditions present in the ice grains of which the CO2 is a part. Depending on the composition of the ice, the CO2 asymmetric stretching band was observed to vary from 2328.7 to 2346.0 cm-1 and have full widths at half-maxima (FWHMs) ranging from 4.7 to 29.9 cm-1. The other CO2 bands showed similar variations. Both position and width are also concentration dependent. Absorption coefficients were determined for the five CO2 bands. These were found to be temperature independent for CO2 in CO and CO2 matrices but varied slightly with temperature for CO2 in H2O-rich ices. For all five bands this variation was found to be less than 15% from 10 to 150 K, the temperature at which H2O ice sublimes. A number of parameters associated with the physical behavior of CO2 in CO2- and H2O-rich ices were also determined. The CO2-CO2 surface binding energy in pure CO2 ices is found to be (delta Hs/k) = 2690 +/- 50 K. CO2-H2O and CO-H2O surface binding energies were determined to be (delta Hs/k) = 2860 +/- 200 K and 1740 +/- 100 K, respectively. Under our experimental conditions, CO2 condenses in measurable quantities into H2O-rich ices at temperatures up to 100 K, only slightly higher than the temperature at which pure CO2 condenses. Once frozen into an H2O-rich ice, the subsequent loss of CO2 upon warming is highly dependent on concentration. For ices with H2O/CO2 > 20, the CO is physically trapped within the H2O lattice, and little CO2 is lost until the sublimation temperature of the H2O matrix is reached. In contrast, in ices having H2O/CO2 < 5, the CO2 remains only to temperatures of about 90 K. Above this point the CO2 readily diffuses out of the H2O matrix. These results suggest that two different forms of H2O lattice are produced. The implications of these data for cometary models and our understanding of cometary formation are considered.     

中纬和热带的中尺度对流系统

文中评述了对中纬和热带的中尺度对流系统的观测研究、数值模拟与理论研究.     

布什维尔德杂岩UG—2铬铁岩层中亲铜元素和铂族元素的分布

绪言 Hiemstra(1985)曾在有关UG—2层的研究中指出,铂族元素浓度的对数值随高度(从铬铁岩底部升高某一距离后的高度)直线下降。铂族元素的这一关系早已由有关元素分馏的瑞利定律所预言。然而,亲铜元素镍和铜的行为并不与此相似,尽管它们与UG—2层和梅林斯基层中的铂族元素通常有着很好的相关关系。这种区分即使存在的话大概也被随后     

Hydrogenated polycyclic aromatic hydrocarbons and the 2940 and 2850 wavenumber (3.40 and 3.51 micron) infrared emission features

The 3150-2700 cm-1 (3.17-3.70 microns) range of the spectra of a number of Ar-matrix-isolated PAHs containing excess H atoms (Hn-PAHs) are presented. This region covers features produced by aromatic and aliphatic C-H stretching vibrations as well as overtone and combination bands involving lower lying fundamentals. The aliphatic C-H stretches in molecules of this type having low to modest excess H coverage provide excellent fits to a number of the weak emission features superposed on the plateau between 3080 and 2700 cm-1 (3.25 and 3.7 microns) in the spectra of many planetary nebulae, reflection nebulae, and H II regions. Higher H coverage is implied for a few objects. We compare these results in context with the other suggested identifications of the emission features in the 2950-2700 cm-1 (3.39-3.70 microns) region and briefly discuss their astrophysical implications.     

Calculations of ion-molecule deuterium fractionation reactions involving HD

Gas-phase chemical models of deuterium fractionation in dense interstellar clouds utilize a small number of exothermic reactions to achieve fractionation. Although HD is a major repository of deuterium, it appears not to exchange deuterium with many molecular ions. Useful semiquantitative reasons have been given for the unusual lack of reactivity of exothermic ion-HD deuterium exchange systems, but quantum chemical studies are needed to understand these ideas in more detail and to determine if the lack of reactivity pertains at very low temperatures not studied in the laboratory, or whether tunneling can drive the reactions. Accordingly, the potential energy surfaces of three representative ion-molecule exchange reactions involving protonated ions (H3+, CH3+, HCO+) and HD have been investigated with ab initio quantum chemical techniques. Our results generally confirm the semiquantitative picture as to which reactions are likely to occur and show that tunneling at low temperatures is unlikely to alter this picture.     

New emission features in the 11-13 micron region and their relationship to polycyclic aromatic hydrocarbons

If the "11.3 microns" emission feature seen in the spectra of many planetary nebulae, H II regions, and reflection nebulae is due to polycyclic aromatic hydrocarbons (PAHs), then additional features should be present between 11.3 and 13.0 microns (885 and 770 cm-1). Moderate-resolution spectra of NGC 7027, HD 44179, IRAS 21282+5050, and BD + 30 degrees 3639 are presented which show that the "11.3 microns" feature actually peaks at 11.22 microns (891 cm-1). The spectra also show evidence of new emission features near 11.9 and 12.7 microns (840 and 787 cm-1). These are consistent with an origin from PAHs and can be used to constrain the molecular structure of the family of PAHs responsible for the infrared features. The observed asymmetry of the "11.3 microns" band is consistent with the slight anharmonicity expected in the C--H out-of-plane bending mode in PAHs. Laboratory experiments show that the intensity of this mode relative to the higher frequency modes depends on the extent of molecular "clustering." The observed strengths of the "11.3 microns" interstellar bands relative to the higher frequency bands are most consistent with the features originating from free molecular PAHs. The intensity and profile of the underlying broad structure, however, may well arise from PAH clusters and amorphous carbon particles. Analysis of the 11-13 microns (910-770 cm-1) emission suggests that the molecular structures of the most intensity emitting free PAHs vary somewhat between the high-excitation environment in NGC 7027 and the low-excitation but high-flux environment close to HD 44179. Finally, a previously undetected series of regularly spaced features between 10 and 11 microns (1000 and 910 cm-1) in the spectrum of HD 44179 suggests that a simple polyatomic hydride is present in the gas phase in this object.