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One of the most efficient ways of producing negative ions is by the process of dissociative electron attachment to molecules. Here, a diatomic or polyatomic molecule dissociates, by the impact of a low energy electron, into component atoms (or smaller molecular species) while the incident electron attaches itself to one of the dissociating fragments.
The main data need for stellar atmosphere and spectrum modeling remains atomic and molecular transition data, particularly energy levels and transition cross-sections. We emphasize that data is needed for bound-free (b - f) as well as bound-bound (b - b), and collisional as well as radiative transitions. Data is now needed for polyatomic molecules as well as atoms, ions, and diatomic molecules. In addition, data for the formation of, and extinction due to, liquid and solid phase dust grains is needed. A prioritization of species and data types is presented, and gives emphasis to Fe group elements, and elements important for the investigation of nucleosynthesis and Galactic chemical evolution, such as the -elements and n-capture elements. Special data needs for topical problems in the modeling of cool stars and brown dwarfs are described.
Mass flow and compositional gradient (elemental and isotope separation) occurs when flu-id(s) or gas(es) in an enclosure is subjected to a thermal gradient, and the phenomenon is named thermal diffusion. Gas phase thermal diffusion has been theoretically and experimentally studied for more than a century, although there has not been a satisfactory theory to date. Nevertheless, for isotopic system, the Chapman-Enskog theory predicts that the mass difference is the only term in the thermal diffusion separation factors that differs one isotope pair to another,with the assumptions that the molecules are spherical and systematic (monoatomic-like structure) and the particle collision is elastic. Our previous report indicates factors may be playing a role because the Non-Mass Dependent (NMD) effect is found for both symmetric and asymmetric, linear and spherical polyatomic molecules over a wide range of temperature (-196C to +237C). The observed NMD phenomenon in the simple thermal-diffusion experiments demands quantitative validation and theoretical explanation. Besides the pressure and temperature dependency illustrated in our previous reports, efforts are made in this study to address issues such as the role of convection or molecular structure and whether it is a transient, non-equilibrium effect only.
Physical processes that unmix elements/isotopes of gas molecules involve phase changes, diffusion (chemical or thermal), effusion and gravitational settling. Some of those play significant roles for the evolution of chemical and isotopic compositions of gases in planetary bodies which lead to better understanding of surface paleoclimatic conditions, e.g. gas bubbles in Antarctic ice, and planetary evolution, e.g. the solar-wind erosion induced gas escaping from exosphere on terrestrial planets.. A mass dependent relationship is always expected for the kinetic isotope fractionations during these simple physical processes, according to the kinetic theory of gases by Chapman, Enskog and others [3-5]. For O-bearing (O16, -O17, -O18) molecules the alpha O-17/ alpha O-18 is expected at 0.5 to 0.515, and for S-bearing (S32,-S33. -S34, -S36) molecules, the alpha S-33/ αlpha S-34 is expected at 0.5 to 0.508, where alpha is the isotope fractionation factor associated with unmixing processes. Thus, one isotope pair is generally proxied to yield all the information for the physical history of the gases. However, we recently] reported the violation of mass law for isotope fractionation among isotope pairs of multiple isotope system during gas diffusion or convection under thermal gradient (Thermal Gradient Induced Non-Mass Dependent effect, TGI-NMD). The mechanism(s) that is responsible to such striking observation remains unanswered. In our past studies, we investigated polyatomic molecules, O2 and SF6, and we suggested that nuclear spin effect could be responsible to the observed NMD effect in a way of changing diffusion coefficients of certain molecules, owing to the fact of negligible delta S-36 anomaly for SF6.. On the other hand, our results also showed that for both diffusion and convection under thermal gradient, this NMD effect is increased by lower gas pressure, bigger temperature gradient and lower average temperature, which indicate that the nuclear spin effect may not be the significant contributor as the energies involved in the hyperfine effect are much smaller than those with molecular collisions, especially under convective conditions.
Starting from the refined Robert-Bonamy formalism [Q. Ma, C. Boulet, and R. H. Tipping, J. Chem. Phys. 139, 034305 (2013)], we propose here an extension of line mixing studies to infrared absorptions of linear polyatomic molecules having stretching and bending modes. The present formalism does not neglect the internal degrees of freedom of the perturbing molecules, contrary to the energy corrected sudden (ECS) modeling, and enables one to calculate the whole relaxation matrix starting from the potential energy surface. Meanwhile, similar to the ECS modeling, the present formalism properly accounts for roles played by all the internal angular momenta in the coupling process, including the vibrational angular momentum. The formalism has been applied to the important case of CO2 broadened by N2. Applications to two kinds of vibrational bands (sigma yields sigma and sigma yields pi) have shown that the present results are in good agreement with both experimental data and results derived from the ECS model.
The diffuse interstellar bands (DIBs) are absorption features observed in optical and near-infrared spectra that are thought to be associated with carbon-rich polyatomic molecules in interstellar gas. However, because the central wavelengths of these bands do not correspond with electronic transitions of any known atomic or molecular species, their nature has remained uncertain since their discovery almost a century ago. Here we report on unusually strong DIBs in optical spectra of the broad- lined Type Ic supernova SN2012ap that exhibit changes in equivalent width over short (. 30 days) timescales. The 4428 A and 6283 A DIB features get weaker with time, whereas the 5780 A feature shows a marginal increase. These nonuniform changes suggest that the supernova is interacting with a nearby source of the DIBs and that the DIB carriers possess high ionization potentials, such as small cations or charged fullerenes. We conclude that moderate-resolution spectra of supernovae with DIB absorptions obtained within weeks of outburst could reveal unique information about the mass-loss environment of their progenitor systems and provide new constraints on the properties of DIB carriers.
An approach to estimate the effective vibrational relaxation time for polyatomic molecules under the context of two-temperature thermochecmial state model is proposed. Landau-Teller vibrational relaxation equation is used as a basis, and vibrational energies are estimated with partition energy functions assuming harmonic oscillator model. A special weighting procedure is presented, and effective vibrational relaxation time is derived. A series of numerical experiments with CO2 and NH3 mixtures is performed, and the aeroheating results are presented. The results of CO2 environment simulations are compared with the vibrational relaxation model of Park et al. [JTHT, 8(1994), pp. 9–23]. The simulations are also conducted with a modified Landau-Teller expression.
Rechargeable aluminum-graphite batteries using chloroaluminate-containing electrolytes have been the focus of significant research, particularly due to their high-rate capabilities. Engineered graphite electrodes have been shown to exhibit supercapacitor-like rate performance, despite the fact they store charge via the electrochemical intercalation of polyatomic AlCl4− anions. However, the origins of such rate capabilities are not well understood. Here, using electrochemical techniques, we disentangle quantitatively the diffusion-limited Faradaic, pseudocapacitive, and capacitive contributions to charge storage, revealing that AlCl4− anions intercalate into graphite with significant pseudocapacitive characteristics due to low ion diffusion limitations. Pristine and mildly exfoliated graphites are compared, where exfoliation resulted in significantly higher pseudocapacitive AlCl4− intercalation at the highest potential redox pair as well as higher galvanostatic capacity retention at faster discharge rates. The relationships between graphite structure, ion mass transport, and the overall rate of electrochemical AlCl4− intercalation are discussed. Ion diffusion within the electrolyte phase of the porous electrode is shown to play a key role in controlling the rate of intercalation at higher potentials and faster rates, which can be enhanced by reducing electrode tortuosity. The results establish that chloroaluminate anion intercalation into graphite exhibits non-diffusion-limited pseudocapacitive contributions that are tunable by modifying the graphite structure.