Fundamental data on the desorption of pure interstellar ices

The desorption of molecular ices from grain surfaces is important in a number of astrophysical environments including dense molecular clouds, cometary nuclei and the surfaces and atmospheres of some planets. With this in mind, we have performed a detailed investigation of the desorption of pure water, pure methanol and pure ammonia ices from a model dust-grain surface. We have used these results to determine the desorption energy, order of desorption and the pre-exponential factor for the desorption of these molecular ices from our model surface. We find good agreement between our desorption energies and those determined previously; however, our values for the desorption orders, and hence also the pre-exponential factors, are different to those reported previously. The kinetic parameters derived from our data have been used to model desorption on time-scales relevant to astrophysical processes and to calculate molecular residence times, given in terms of population half-life as a function of temperature. These results show the importance of laboratory data for the understanding of astronomical situations whereby icy mantles are warmed by nearby stars and by other dynamical events

The influence of steps on the dissociation of NO on Pt surfaces: Temperature-programmed desorption studies of NO adsorption on Pt{211}

Temperature-programmed desorption (TPD) has been used to investigate the adsorption of NO on Pt{211} at 300 K and 120 K. Results show that NO dissociation occurs readily on Pt{211}, as evidenced by the observation of N-2 and N2O in the TPD spectrum. Following adsorption at 120 K three NO TPD peaks at 338, 416, and 503 K are observed, in agreement with previous observations. In combination with data acquired in a recent reflection absorption infrared spectroscopy and density functional theory investigation of NO/Pt{211}, these peaks are assigned to the desorption of NO from an O-NO complex, the recombinative desorption of N and O atoms, and to desorption of a step-bridged NO species, respectively. These assignments are in disagreement with previous work, where the high-temperature NO peak was assigned to the desorption of step bound NO and the two low-temperature peaks were assigned to the desorption of NO from terrace sites. TPD spectra recorded following adsorption at 300 K, with a heating rate of 1 K s(-1), show similar features to those recorded following 120 K adsorption. This is also in disagreement with previous observations, where only two NO TPD peaks were observed following adsorption at room temperature. This disagreement can be accounted for by the different heating rates used in the two experiments. (C) 2003 American Institute of Physics

Difficult Problems Having Easy Solutions

We discuss how a class of difficult kinematic problems can play an important role in an introductory course in stimulating students' reasoning on more complex physical situations. The problems presented here have an elementary analysis once certain symmetry features of the motion are revealed. We also explore some unexpected directions these problems lead us.Comment: Latex 2 pages, 2 figure

Gapless Excitation above a Domain Wall Ground State in a Flat Band Hubbard Model

We construct a set of exact ground states with a localized ferromagnetic domain wall and with an extended spiral structure in a deformed flat-band Hubbard model in arbitrary dimensions. We show the uniqueness of the ground state for the half-filled lowest band in a fixed magnetization subspace. The ground states with these structures are degenerate with all-spin-up or all-spin-down states under the open boundary condition. We represent a spin one-point function in terms of local electron number density, and find the domain wall structure in our model. We show the existence of gapless excitations above a domain wall ground state in dimensions higher than one. On the other hand, under the periodic boundary condition, the ground state is the all-spin-up or all-spin-down state. We show that the spin-wave excitation above the all-spin-up or -down state has an energy gap because of the anisotropy.Comment: 26 pages, 1 figure. Typos are fixe

Applying laboratory thermal desorption data in an interstellar context: sublimation of methanol thin films

Methods by which experimental measurements of thermal desorption can be applied in astrophysical environments have been developed, using the sublimation of solid methanol as an example. The temperature programmed desorption of methanol from graphitic, amorphous silica and polycrystalline gold substrates was compared, with the kinetic parameters of desorption extracted by either a leading edge analysis or by fitting using a stochastic integration method. At low coverages, the desorption shows a substrate-dependent fractional order. However, at higher coverages methanol desorption is zeroth order with kinetic parameters independent of substrate. Using a kinetic model based on the stochastic integration analyses, desorption under astrophysically relevant conditions can be simulated. We find that the chemical and morphological nature of the substrate has relatively little impact on the desorption temperature of solid methanol, and that the substrate independent zeroth-order kinetics can provide a satisfactory model for desorption in astrophysical environments. Uncertainties in the heating rate and the distribution of grain sizes will have the largest influence on the range of desorption temperature. These conclusions are likely to be generally applicable to all species in dust grain ice mantles

Collision Dynamics and Solvation of Water Molecules in a Liquid Methanol Film

Environmental molecular beam experiments are used to examine water interactions with liquid methanol films at temperatures from 170 K to 190 K. We find that water molecules with 0.32 eV incident kinetic energy are efficiently trapped by the liquid methanol. The scattering process is characterized by an efficient loss of energy to surface modes with a minor component of the incident beam that is inelastically scattered. Thermal desorption of water molecules has a well characterized Arrhenius form with an activation energy of 0.47{\pm}0.11 eV and pre-exponential factor of 4.6 {\times} 10^(15{\pm}3) s^(-1). We also observe a temperature dependent incorporation of incident water into the methanol layer. The implication for fundamental studies and environmental applications is that even an alcohol as simple as methanol can exhibit complex and temperature dependent surfactant behavior.Comment: 8 pages, 5 figure

Grain Surface Models and Data for Astrochemistry

AbstractThe cross-disciplinary field of astrochemistry exists to understand the formation, destruction, and survival of molecules in astrophysical environments. Molecules in space are synthesized via a large variety of gas-phase reactions, and reactions on dust-grain surfaces, where the surface acts as a catalyst. A broad consensus has been reached in the astrochemistry community on how to suitably treat gas-phase processes in models, and also on how to present the necessary reaction data in databases; however, no such consensus has yet been reached for grain-surface processes. A team of ∼25 experts covering observational, laboratory and theoretical (astro)chemistry met in summer of 2014 at the Lorentz Center in Leiden with the aim to provide solutions for this problem and to review the current state-of-the-art of grain surface models, both in terms of technical implementation into models as well as the most up-to-date information available from experiments and chemical computations. This review builds on the results of this workshop and gives an outlook for future directions

Peeling the astronomical onion

Water ice is the most abundant solid in the Universe. Understanding the formation, structure and multiplicity of physicochemical roles for water ice in the cold, dense interstellar environments in which it is predominantly observed is a crucial quest for astrochemistry as these are regions active in star and planet formation. Intuitively, we would expect the mobility of water molecules deposited or synthesised on dust grain surfaces at temperatures below 50 K to be very limited. This work delves into the thermally-activated mobility of H2O molecules on model interstellar grain surfaces. The energy required to initiate this process is studied by reflection-absorption infrared spectroscopy of small quantities of water on amorphous silica and highly oriented pyrolytic graphite surfaces as the surface is annealed. Strongly non-Arrhenius behaviour is observed with an activation energy of 2 kJ mol-1 on the silica surface below 25 K and 0 kJ mol-1 on both surfaces between 25 and 100 K. The astrophysical implication of these results is that on timescales shorter than that estimated for the formation of a complete monolayer of water ice on a grain, aggregation of water ice will result in a non-uniform coating of water, hence leaving bare grain surface exposed. Other molecules can thus be formed or adsorbed on this bare surface

Probing model interstellar grain surfaces with small molecules

Temperature-programmed desorption and reflection-absorption infrared spectroscopy have been used to explore the interaction of oxygen (O2), nitrogen (N2), carbon monoxide (CO) and water (H2O) with an amorphous silica film as a demonstration of the detailed characterization of the silicate surfaces that might be present in the interstellar medium. The simple diatomic adsorbates are found to wet the silica surface and exhibit first-order desorption kinetics in the regime up to monolayer coverage. Beyond that, they exhibit zero-order kinetics as might be expected for sublimation of bulk solids. Water, in contrast, does not wet the silica surface and exhibits zero-order desorption kinetics at all coverages consistent with the formation of an islanded structure. Kinetic parameters for use in astrophysical modelling were obtained by inversion of the experimental data at sub-monolayer coverages and by comparison with models in the multilayer regime. Spectroscopic studies in the sub-monolayer regime show that the C–O stretching mode is at around 2137 cm−1 (5.43 μm), a position consistent with a linear surface–CO interaction, and is inhomogenously broadened as resulting from the heterogeneity of the surface. These studies also reveal, for the first time, direct evidence for the thermal activation of diffusion, and hence de-wetting, of H2O on the silica surface. Astrophysical implications of these findings could account for a part of the missing oxygen budget in dense interstellar clouds, and suggest that studies of the sub-monolayer adsorption of these simple molecules might be a useful probe of surface chemistry on more complex silicate materials