Pore evolution in interstellar ice analogues: simulating the effects of temperature increase

Context. The level of porosity of interstellar ices - largely comprised of amorphous solid water (ASW) - contains clues on the trapping capacity of other volatile species and determines the surface accessibility that is needed for solid state reactions to take place. Aims. Our goal is to simulate the growth of amorphous water ice at low temperature (10 K) and to characterize the evolution of the porosity (and the specific surface area) as a function of temperature (from 10 to 120 K). Methods. Kinetic Monte Carlo simulations are used to mimic the formation and the thermal evolution of pores in amorphous water ice. We follow the accretion of gas-phase water molecules as well as their migration on surfaces with different grid sizes, both at the top growing layer and within the bulk. Results. We show that the porosity characteristics change substantially in water ice as the temperature increases. The total surface of the pores decreases strongly while the total volume decreases only slightly for higher temperatures. This will decrease the overall reaction efficiency, but in parallel, small pores connect and merge, allowing trapped molecules to meet and react within the pores network, providing a pathway to increase the reaction efficiency. We introduce pore coalescence as a new solid state process that may boost the solid state formation of new molecules in space and has not been considered so far.Comment: 9 pages, 8 figures Accepted for publication in A&

Variations of the Mid-IR Aromatic Features Inside and Among Galaxies

We present the results of a systematic study of mid-IR spectra of Galactic regions, Magellanic HII regions, and galaxies of various types (dwarf, spiral, starburst), observed by the satellites ISO and Spitzer. We study the relative variations of the 6.2, 7.7, 8.6 and 11.3 micron features inside spatially resolved objects (such as M82, M51, 30 Doradus, M17 and the Orion Bar), as well as among 90 integrated spectra of 50 objects. Our main results are that the 6.2, 7.7 and 8.6 micron bands are essentially tied together, while the ratios between these bands and the 11.3 micron band varies by one order of magnitude. This implies that the properties of the PAHs are remarkably universal throughout our sample, and that the relative variations of the band ratios are mainly controled by the fraction of ionized PAHs. In particular, we show that we can rule out both the modification of the PAH size distribution, and the mid-infrared extinction, as an explanation of these variations. Using a few well-studied Galactic regions (including the spectral image of the Orion Bar), we give an empirical relation between the I(6.2)/I(11.3) ratio and the ionization/recombination ratio G0/ne.Tgas^0.5, therefore providing a useful quantitative diagnostic tool of the physical conditions in the regions where the PAH emission originates. Finally, we discuss the physical interpretation of the I(6.2)/I(11.3) ratio, on galactic size scales.Comment: Accepted by the ApJ, 67 pages, 70 figure

Oxygen diffusion and reactivity at low temperature on bare amorphous olivine-type silicate

The mobility of O atoms at very low temperatures is not generally taken into account, despite O diffusion would add to a series of processes leading to the observed rich molecular diversity in space. We present a study of the mobility and reactivity of O atoms on an amorphous silicate surface. Our results are in the form of RAIRS and temperature-programmed desorption spectra of O2 and O3 produced via two pathways: O + O and O2 + O, investigated in a submonolayer regime and in the range of temperature between 6.5 and 30 K. All the experiments show that ozone is formed efficiently on silicate at any surface temperature between 6.5 and 30 K. The derived upper limit for the activation barriers of O + O and O2 + O reactions is 150 K/kb. Ozone formation at low temperatures indicates that fast diffusion of O atoms is at play even at 6.5 K. Through a series of rate equations included in our model, we also address the reaction mechanisms and show that neither the Eley Rideal nor the Hot atom mechanisms alone can explain the experimental values. The rate of diffusion of O atoms, based on modeling results, is much higher than the one generally expected, and the diffusive process proceeds via the Langmuir-Hinshelwood mechanism enhanced by tunnelling. In fact, quantum effects turn out to be a key factor that cannot be neglected in our simulations. Astrophysically, efficient O3 formation on interstellar dust grains would imply the presence of huge reservoirs of oxygen atoms. Since O3 is a reservoir of elementary oxygen, and also of OH via its hydrogenation, it could explain the observed concomitance of CO2 and H2O in the ices.Comment: 28 pages, 14 figure

Methanol in the sky with diamonds

The present of gas phase methanol in dense interstellar molecular clouds was established by radio detection of its rotational emission lines. However, the position, width, and profile of a absorption band near 1470 cm(exp -1) in the IR spectra of many dense molecular clouds strongly suggests that solid methanol is an important component of interstellar ices. In an attempt to better constrain the identification of 1470 cm(exp -1) feature, we began a program to search for other characteristic absorption bands of solid state methanol in the spectra of objects known to produce this band. One such feature is now identified in the spectra of several dense molecular clouds and its position, width, and profile fit well with those of laboratory H2O:CH3OH ices. Thus, the presence of methanol-bearing ices in space is confirmed

Molecular hydrogen formation in the interstellar medium

We have developed a model for molecular hydrogen formation under astrophysically relevant conditions. This model takes fully into account the presence of both physisorbed and chemisorbed sites on the surface, allows quantum mechanical diffusion as well as thermal hopping for absorbed H-atoms, and has been benchmarked versus recent laboratory experiments on H2 formation on silicate surfaces. The results show that H2 formation on grain surface is efficient in the interstellar medium up to some 300K. At low temperatures (<100K), H2 formation is governed by the reaction of a physisorbed H with a chemisorbed H. At higher temperatures, H2 formation proceeds through reaction between two chemisorbed H atoms. We present simple analytical expressions for H2 formation which can be adopted to a wide variety of surfaces once their surfaces characteristics have been determined experimentally.Comment: 4 pages, 1 figur

Laboratory and observational study of the interrelation of the carbonaceous component of interstellar dust and solar system materials

By studying the chemical and isotopic composition of interstellar ice and dust, one gains insight into the composition and chemical evolution of the solid bodies in the solar nebula and the nature of the material subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to spectroscopically probe the composition of interstellar ice and dust in the mid-infrared, the spectral range which is most diagnostic of fundamental molecular vibrations. We can compare these spectra of various astronomical objects (including the diffuse and dense interstellar medium, comets, and the icy outer planets and their satellites) with the spectra of analogs we produce in the laboratory under conditions which mimic those in these different objects. In this way one can determine the composition and abundances of the major constituents of the various ices and place general constraints on the types of organics coating the grains in the diffuse interstellar medium. In particular we have shown the ices in the dense clouds contain H2O, CH3OH, CO, perhaps some NH3 and H2CO, we well as nitriles and ketones or esters. Furthermore, by studying the photochemistry of these ice analogs in the laboratory, one gains insight into the chemistry which takes place in interstellar/precometary ices. Chemical and spectroscopic studies of photolyzed analogs (including deuterated species) are now underway. The results of some of these studies will be presented and implications for the evolution of the biogenic elements in interstellar dust and comets will be discussed

Direct estimation of electron density in the Orion Bar PDR from mm-wave carbon recombination lines

A significant fraction of the molecular gas in star-forming regions is irradiated by stellar UV photons. In these environments, the electron density (n_e) plays a critical role in the gas dynamics, chemistry, and collisional excitation of certain molecules. We determine n_e in the prototypical strongly irradiated photodissociation region (PDR), the Orion Bar, from the detection of new millimeter-wave carbon recombination lines (mmCRLs) and existing far-IR [13CII] hyperfine line observations. We detect 12 mmCRLs (including alpha, beta, and gamma transitions) observed with the IRAM 30m telescope, at ~25'' angular resolution, toward the H/H2 dissociation front (DF) of the Bar. We also present a mmCRL emission cut across the PDR. These lines trace the C+/C/CO gas transition layer. As the much lower frequency carbon radio recombination lines, mmCRLs arise from neutral PDR gas and not from ionized gas in the adjacent HII region. This is readily seen from their narrow line profiles (dv=2.6+/-0.4 km/s) and line peak LSR velocities (v_LSR=+10.7+/-0.2 km/s). Optically thin [13CII] hyperfine lines and molecular lines - emitted close to the DF by trace species such as reactive ions CO+ and HOC+ - show the same line profiles. We use non-LTE excitation models of [13CII] and mmCRLs and derive n_e = 60-100 cm^-3 and T_e = 500-600 K toward the DF. The inferred electron densities are high, up to an order of magnitude higher than previously thought. They provide a lower limit to the gas thermal pressure at the PDR edge without using molecular tracers. We obtain P_th > (2-4)x10^8 cm^-3 K assuming that the electron abundance is equal or lower than the gas-phase elemental abundance of carbon. Such elevated thermal pressures leave little room for magnetic pressure support and agree with a scenario in which the PDR photoevaporates.Comment: Accepted for publication in A&A Letters (includes language editor corrections