Surface Of Dust Grains Research Articles

Chemistry and radiative transfer of water in cold, dense clouds

The Herschel Space Observatory's recent detections of water vapor in the cold, dense cloud L1544 allow a direct comparison between observations and chemical models for oxygen species in conditions just before star formation. We explain a chemical model for gas phase water, simplified for the limited number of reactions or processes that are active in extreme cold ($<$ 15 K). In this model, water is removed from the gas phase by freezing onto grains and by photodissociation. Water is formed as ice on the surface of dust grains from O and OH and released into the gas phase by photodesorption. The reactions are fast enough with respect to the slow dynamical evolution of L1544 that the gas phase water is in equilibrium for the local conditions thoughout the cloud. We explain the paradoxical radiative transfer of the H$_2$O ($1_{10}-1_{01}$) line. Despite discouragingly high optical depth caused by the large Einstein A coefficient, the subcritical excitation in the cold, rarefied H$_2$ causes the line brightness to scale linearly with column density. Thus the water line can provide information on the chemical and dynamical processes in the darkest region in the center of a cold, dense cloud. The inverse P-Cygni profile of the observed water line generally indicates a contracting cloud. This profile is reproduced with a dynamical model of slow contraction from unstable quasi-static hydrodynamic equilibrium (an unstable Bonnor-Ebert sphere).

H2FORMATION IN DIFFUSE CLOUDS: A NEW KINETIC MONTE CARLO STUDY

We used the continuous-time random-walk Monte Carlo technique to study anew the formation of H2 on the surfaces of interstellar dust grains in diffuse interstellar clouds. For our study, we considered three different grain materials, olivine (a polycrystalline silicate), amorphous silicate, and amorphous carbon, as well as a grain temperature that depends on granular size. For some runs, we included temperature fluctuations. Four different granular surfaces were used, one with one type of binding site due to physisorption, one with five different types of physisorption binding sites due to lateral forces, and two with sites for chemisorption, one in which chemisorption sites are entered through precursor physisorption sites, and one in which chemisorption is direct but occurs with a barrier for the adsorption of the first hydrogen atom. We found that on flat and rough olivine surfaces, molecular hydrogen is formed at low efficiencies, with smaller grains contributing very little despite their large numbers due to high temperatures. For flat amorphous carbon and amorphous silicate surfaces, the efficiency increases, reaching unity for the largest grains. For models with barrierless chemisorption, the efficiency of formation of H2 is near unity at all grain sizes considered, while for direct chemisorption via a barrier, we found efficiencies of 0.13-0.6 depending upon the barrier, but independent of grain size. Treating the flat olivine and amorphous silicate surfaces with temperature fluctuations increases the efficiency of H2 formation.

FORMATION OF SILICON OXIDE GRAINS AT LOW TEMPERATURE

The formation of grains in the interstellar medium, i.e., at low temperature, has been proposed as a possibility to solve the lifetime problem of cosmic dust. This process lacks a firm experimental basis, which is the goal of this study. We have investigated the condensation of SiO molecules at low temperature using neon matrix and helium droplet isolation techniques. The energies of SiO polymerization reactions have been determined experimentally with a calorimetric method and theoretically with calculations based on the density functional theory. The combined experimental and theoretical values have revealed the formation of cyclic (SiO)$_k$ ($k$ = 2--3) clusters inside helium droplets at $T$ = 0.37 K. Therefore, the oligomerization of SiO molecules is found to be barrierless and is expected to be fast in the low-temperature environment of the interstellar medium on the surface of dust grains. The incorporation of numerous SiO molecules in helium droplets leads to the formation of nanoscale amorphous SiO grains. Similarly, the annealing and evaporation of SiO-doped Ne matrices lead to the formation of solid amorphous SiO on the substrate. The structure and composition of the grains were determined by infrared absorption spectroscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. Our results support the hypothesis that interstellar silicates \textbf{can be formed} in the low temperature regions of the interstellar medium by accretion through barrierless reactions.

Electrostatic activation of prebiotic chemistry in substellar atmospheres

AbstractCharged dust grains in the atmospheres of exoplanets may play a key role in the formation of prebiotic molecules, necessary to the origin of life. Dust grains submerged in an atmospheric plasma become negatively charged and attract a flux of ions that are accelerated from the plasma. The energy of the ions upon reaching the grain surface may be sufficient to overcome the activation energy of particular chemical reactions that would be unattainable via ion and neutral bombardment from classical, thermal excitation. As a result, prebiotic molecules or their precursors could be synthesized on the surface of dust grains that form clouds in exoplanetary atmospheres. This paper investigates the energization of the plasma ions, and the dependence on the plasma electron temperature, in the atmospheres of substellar objects such as gas giant planets. Calculations show that modest electron temperatures of ≈1 eV (≈104 K) are enough to accelerate ions to sufficient energies that exceed the activation energies required for the formation of formaldehyde, ammonia, hydrogen cyanide and the amino acid glycine.

Simulating the D/H ratio of water formed in the early solar nebula

Our solar system originated from a protoplanetary disk about 4.6 billion years ago. We simulate the formation of this disk by a three-stage model of the solar nebula (SN) which describes the hydrodynamic and chemical evolution of a cold cloud core consisting of gas and one mass percent dust. Considering the first two stages of this SN-model we have studied the formation and deuteration of water, which is an important precondition of life. During the quasi-stationary stage of the cloud core, corresponding to the first SN stage, water has been formed on the surface of dust grains by the hydrogenation of oxygen. The gas and dust temperatures, which differ at the outer boundary of the core, are nearly 14 K and reach 9 K in its center. Therefore an icy mantle forms on the dust grains in less than 105 years and changes slowly afterwards. Because of the large abundance of hydrogen and a carbon to oxygen (C/O) ratio of 0.44 the major component of this mantle is water ice. We found that the water produced in the gas phase amounts to less than 20 ppm of the water formed on dust grains. In both phases, the deuterium enrichment δD (‰) relative to the Standard Mean Ocean Water varies at 1 AU from 15,050 to 63,100‰ (or a D/H ratio from 2 to 0.5%) and indicates the low formation temperature of water molecules. In the second stage of our SN-model, the collapse of the cold cloud core is simulated using a semi-analytical solution of the magneto-hydrodynamic equations. Due to relatively high temperatures around the center (10^(2-3) K), this range is identified with the hot corino observed in regions of low mass star formation in our galaxy. There, the icy mantles of the grains vanish due to desorption of water molecules from their surfaces. As a result the water to hydrogen ratio in the gas phase increases to 10^(-5)-10^(-4). Since this water was formed in a cold region and a collision related destruction of water molecules (occurring at ~10^5 K) can be neglected everywhere except for the protostellar source in the core center (< 10^(-2) AU), the deuterium enrichment in the outer hot corino (1 AU) reaches δD of 2,210‰ (or D/H of 0.1%) at the end of the main collapse phase. Different reasons for this relatively high value are discussed.

Characterizing the chemical pathways for water formation--a deep search for hydrogen peroxide.

In 2011, hydrogen peroxide (HOOH) was observed for the first time outside the solar system (Bergman et al., Astron. Astrophys., 2011, 531, L8). This detection appeared a posteriori to be quite natural, as HOOH is an intermediate product in the formation of water on the surface of dust grains. Following up on this detection, we present a search for HOOH in a diverse sample of sources in different environments, including low-mass protostars and regions with very high column densities, such as Infrared Dark Clouds (IRDCs). We do not detect the molecule in any other source than Oph A, and derive 3sigma upper limits for the abundance of HOOH relative to H2 lower than that in Oph A for most sources. This result sheds a different light on our understanding of the detection of HOOH in Oph A, and shifts the question of why this source seems to be special. Therefore we rediscuss the detection of HOOH in Oph A, as well as the implications of the low abundance of HOOH, and its similarity with the case of O2. Our chemical models show that the production of HOOH is extremely sensitive to temperature, and is favored only in the range 20-30 K. The relatively high abundance of HOOH observed in Oph A suggests that the bulk of the material lies at a temperature in the range 20-30 K.

Calculation of the composition of the equilibrium dusty plasma

We consider the equilibrium dusty plasma consisting of neutral atoms of the gas, the gas ions, free electrons and charged dust particles. We obtained the generalized Saha-equation for equilibrium dusty plasmas. In the approximation of a rectangular potential well at the surface of dust grains are calculated charge of the dust particles, the concentration of ions and electrons. It is shown that depending on the basic parameters of the plasma charged dust particles can be both positive and negative.

THREE-DIMENSIONAL, OFF-LATTICE MONTE CARLO KINETICS SIMULATIONS OF INTERSTELLAR GRAIN CHEMISTRY AND ICE STRUCTURE

The first off-lattice Monte Carlo kinetics model of interstellar dust-grain surface chemistry is presented. The positions of all surface particles are determined explicitly, according to the local potential minima resulting from the pair-wise interactions of contiguous atoms and molecules, rather than by a pre-defined lattice structure. The model is capable of simulating chemical kinetics on any arbitrary dust-grain morphology, as determined by the user-defined positions of each individual dust-grain atom. A simple method is devised for the determination of the most likely diffusion pathways and their associated energy barriers for surface species. The model is applied to a small, idealized dust grain, adopting various gas densities and using a small chemical network. Hydrogen and oxygen atoms accrete onto the grain, to produce H2O, H2, O2 and H2O2. The off-lattice method allows the ice structure to evolve freely; ice mantle porosity is found to be dependent on the gas density, which controls the accretion rate. A gas density of 2 x 10^{4} cm^{-3}, appropriate to dark interstellar clouds, is found to produce a fairly smooth and non-porous ice mantle. At all densities, H2 molecules formed on the grains collect within the crevices that divide nodules of ice, and within micropores (whose extreme inward curvature produces strong local potential minima). The larger pores produced in the high-density models are not typically filled with H2. Direct deposition of water molecules onto the grain indicates that amorphous ices formed in this way may be significantly more porous than interstellar ices that are formed by surface chemistry.

EVIDENCE FOR H2FORMATION DRIVEN DUST GRAIN ALIGNMENT IN IC 63

In the interstellar medium (ISM), molecular hydrogen is expected to form almost exclusively on the surfaces of dust grains. Due to that molecule's large formation energy (–4.5 eV), several dynamical effects are likely associated with the process, including the alignment of asymmetric dust grains with the ambient magnetic field. Such aligned dust grains are, in turn, believed to cause the broadband optical/infrared polarization observed in the ISM. Here, we present the first observational evidence for grain alignment driven by H2 formation, by showing that the polarization of the light from stars behind the reflection nebula IC 63 appears to correlate with the intensity of H2 fluorescence. While our results strongly suggest a role for Purcell rockets in grain alignment, additional observations are needed to conclusively confirm their role. By showing a direct connection between H2 formation and a probe of the dust characteristics, these results also provide one of the first direct confirmations of the grain-surface formation of H2. We compare our observations to ab initio modeling based on Radiative Torque Alignment (RAT) theory.

DISCOVERY OF METHYL ACETATE AND GAUCHE ETHYL FORMATE IN ORION

We report on the discovery of methyl acetate, CH3COOCH3, through the detection of a large number of rotational lines from each one of the spin states of the molecule: AA species (A1 or A2), EA species (E1), AE species (E2), EE species (E3 or E4). We also report the detection, for the first time in space, of the $gauche$ conformer of ethyl formate, CH3CH2OCOH, in the same source. The trans conformer is also detected for the first time outside the galactic center source SgrB2. From the derived velocity of the emission of methyl acetate we conclude that it arises mainly from the compact ridge region with a total column density of (4.2+-0.5)E15 cm(-2). The derived rotational temperature is 150 K. The column density for each conformer of ethyl formate, trans and gauche, is (4.5+-1.0)E14 cm(-2). Their abundance ratio indicates a kinetic temperature of 135 K for the emitting gas and suggests that gas phase reactions could participate efficiently in the formation of both conformers in addition to cold ice mantle reactions on the surface of dust grains.

Insights into H 2 formation in space from ab initio molecular dynamics

Hydrogen formation is a key process for the physics and the chemistry of interstellar clouds. Molecular hydrogen is believed to form on the carbonaceous surface of dust grains, and several mechanisms have been invoked to explain its abundance in different regions of space, from cold interstellar clouds to warm photon-dominated regions. Here, we investigate direct (Eley-Rideal) recombination including lattice dynamics, surface corrugation, and competing H-dimers formation by means of ab initio molecular dynamics. We find that Eley-Rideal reaction dominates at energies relevant for the interstellar medium and alone may explain observations if the possibility of facile sticking at special sites (edges, point defects, etc.) on the surface of the dust grains is taken into account.

Collision and recombination driven instabilities in variable charged dusty plasmas

The dust-acoustic instability driven by recombination of electrons and ions on the surface of charged and variably-charged dust grains as well as by collisions in dusty plasmas with significant pressure of background neutrals have been theoretically investigated. The recombination driven instability is shown to be dominant in the long wavelength regime even in the presence of dust-neutral and ion-neutral collisions, while in the shorter wavelength regime, the dust-neutral collision is found to play a major role. In an earlier research work, the dust-neutral collision was neglected in comparison to the effect due to the recombination for estimating the dust-acoustic instability; later the other report shows that the recombination effect is negligible in the presence of dust-neutral collisions. In line of this present situation our investigation revealed that the recombination is more important than dust-neutral collisions in laboratory plasma and fusion plasma, while the dust-neutral collision frequency is dominant in the interstellar plasmas. The effects of ion and dust densities and ion streaming on the recombination and collision driven mode in parameter regimes relevant for many experimental studies on dusty plasmas have also been calculated.

Water formation at low temperatures by surface O2 hydrogenation III: Monte Carlo simulation

Water is the most abundant molecule found in interstellar icy mantles. In space it is thought to be efficiently formed on the surfaces of dust grains through successive hydrogenation of O, O2 and O3. The underlying physico-chemical mechanisms have been studied experimentally in the past decade and in this paper we extend this work theoretically, using Continuous-Time Random-Walk Monte Carlo simulations to disentangle the different processes at play during hydrogenation of molecular oxygen. CTRW-MC offers a kinetic approach to compare simulated surface abundances of different species to the experimental values. For this purpose, the results of four key experiments-sequential hydrogenation as well as co-deposition experiments at 15 and 25 K-are selected that serve as a reference throughout the modeling stage. The aim is to reproduce all four experiments with a single set of parameters. Input for the simulations consists of binding energies as well as reaction barriers (activation energies). In order to understand the influence of the parameters separately, we vary a single process rate at a time. Our main findings are: (i) The key reactions for the hydrogenation route starting from O2 are H + O2, H + HO2, OH + OH, H + H2O2, H + OH. (ii) The relatively high experimental abundance of H2O2 is due to its slow destruction. (iii) The large consumption of O2 at a temperature of 25 K is due to a high hydrogen diffusion rate. (iv) The diffusion of radicals plays an important role in the full reaction network. The resulting set of 'best fit' parameters is presented and discussed for use in future astrochemical modeling.

DISCOVERY OF THE METHOXY RADICAL, CH 3 O, TOWARD B1: DUST GRAIN AND GAS-PHASE CHEMISTRY IN COLD DARK CLOUDS

We report on the discovery of the methoxy radical (CH3O) toward the cold and dense core B1-b based on the observation, with the IRAM 30 m radio telescope, of several lines at 3 and 2 mm wavelengths. Besides this new molecular species we also report on the detection of many lines arising from methyl mercaptan (CH3SH), formic acid (HCOOH), propynal (HCCCHO), acetaldehyde (CH3CHO), dimethyl ether (CH3OCH3), methyl formate (CH3OCOH), and the formyl radical (HCO). The column density of all these species is 1012 cm–2, corresponding to abundances of 10–11. The similarity in abundances for all these species strongly suggest that they are formed on the surface of dust grains and ejected to the gas phase through non-thermal desorption processes, most likely cosmic rays or secondary photons. Nevertheless, laboratory experiments indicate that the CH3O isomer released to the gas phase is CH2OH rather than the methoxy one. Possible gas-phase formation routes to CH3O from OH and methanol are discussed.

Arbitrary amplitude dust-acoustic double-layers in an electron-depleted dusty plasma with two high-energy tail ion distributions

AbstractArbitrary amplitude dust-acoustic double-layers (DA-DLs) in two high-energy tail ion distributions are investigated. The electron number density has been assumed sufficiently depleted during the charging of dust grains on account of the attachment of background plasma electrons on the surface of dust grains. It is found that under certain conditions DA-DLs may be admitted. The degree of suprathermality of the low-temperature component has a sensitive role on their formation and a small change in this degree can even prevent the DL formation. The ‘Maxwellianization’ of the high-temperature component involves a suprathermalization process of the low-temperature component for the existence of localized DA-DLs. Our results may be relevant to a number of space dusty plasma systems, particularly the Saturn's F-ring where electron depletion and suprathermality are thought to come into play.

KINETIC MONTE CARLO STUDIES OF H2FORMATION ON GRAIN SURFACES OVER A WIDE TEMPERATURE RANGE

We have used the continuous-time random-walk Monte Carlo technique to study the formation of H{sub 2} from two hydrogen atoms on the surface of interstellar dust grains with both physisorption and chemisorption sites on olivine and carbonaceous material. In our standard approach, atoms must first enter the physisorption site before chemisorption can occur. We have considered hydrogen atom mobility due to both thermal hopping and quantum mechanical tunneling. The temperature range between 5 K and 825 K has been explored for different incoming H fluxes representative of interstellar environments with atomic hydrogen number density ranging between 0.1 cm{sup -3} and 100 cm{sup -3} and dust grain sizes ranging from 100 sites to 10{sup 6} sites, the latter corresponding roughly to olivine grains of radius 0.2 {mu}m. In addition, we have also considered rough surfaces with multiple binding sites. Tunneling is found to dominate the surface chemistry at low temperature, but as the temperature increases, the scenario changes. The inclusion of chemisorption sites can provide a meaningful efficiency for H{sub 2} production up to temperatures as high as 700 K depending upon the depth of the chemisorption well. We found that over virtually the entire temperature range studied, the use ofmore » rate equations overestimates the H{sub 2} formation rate to some extent. This overestimate is large at high temperatures, due to very low surface residence times. We have also considered models in which chemisorption sites are entered directly and diffusion proceeds only to other chemisorption sites.« less

Detection of the hydroperoxyl radical HO2towardρOphiuchi A

Context. Hydrogen peroxide (HOOH) was recently detected toward ρ Oph A. Subsequent astrochemical modeling that included reactions in the gas phase and on the surface of dust grains was able to explain the observed abundance, and highlighted the importance of grain chemistry in the formation of HOOH as an intermediate product in water formation. This study also predicted that the hydroperoxyl radical HO2, the precursor of HOOH, should be detectable.

OBSERVATIONAL CONSTRAINTS ON METHANOL PRODUCTION IN INTERSTELLAR AND PREPLANETARY ICES

Methanol (CH3OH) is thought to be an important link in the chain of chemical evolution that leads from simple diatomic interstellar molecules to complex organic species in protoplanetary disks that may be delivered to the surfaces of Earthlike planets. Previous research has shown that CH3OH forms in the interstellar medium predominantly on the surfaces of dust grains. To enhance our understanding of the conditions that lead to its efficient production, we assemble a homogenized catalog of published detections and limiting values in interstellar and preplanetary ices for both CH3OH and the other commonly observed C- and O-bearing species, H2O, CO, and CO2. We use this catalog to investigate the abundance of ice-phase CH3OH in environments ranging from dense molecular clouds to circumstellar envelopes around newly born stars of low and high mass. Results show that CH3OH production arises during the CO freezeout phase of ice-mantle growth in the clouds, after an ice layer rich in H2O and CO2 is already in place on the dust, in agreement with current astrochemical models. The abundance of solid-phase CH3OH in this environment is sufficient to account for observed gas-phase abundances when the ices are subsequently desorbed in the vicinity of embedded stars. CH3OH concentrations in the ices toward embedded stars show order-of-magnitude object-to-object variations, even in a sample restricted to stars of low mass associated with ices lacking evidence of thermal processing. We hypothesize that the efficiency of CH3OH production in dense cores and protostellar envelopes is mediated by the degree of prior CO depletion.

ON WATER FORMATION IN THE INTERSTELLAR MEDIUM: LABORATORY STUDY OF THE O+D REACTION ON SURFACES

In the interstellar medium (ISM), an important channel of water formation is the reaction of atoms on the surface of dust grains. Here, we report on a laboratory study of the formation of water via the O+D reaction network. While prior studies were done on ices, as appropriate to the formation of water in dense clouds, we explored how water formation occurs on bare surfaces, i.e., in conditions mimicking the transition from diffuse to dense clouds (Av ~ 1-5). Reaction products were detected during deposition and afterward when the sample is brought to a high temperature. We quantified the formation of water and intermediary products, such as D2O2, over a range of surface temperatures (15-25 K). The detection of OD on the surface signals the importance of this reactant in the overall scheme of water formation in the ISM.

H2CO in the Horsehead PDR: photo-desorption of dust grain ice mantles

Aims: For the first time we investigate the role of the grain surface chemistry in the Horsehead Photo-dissociation region (PDR). Methods: We performed deep observations of several H2CO rotational lines toward the PDR and its associated dense-core in the Horsehead nebula, where the dust is cold ($\Td \simeq 20-30$ K). We complemented these observations with a map of the p-H2CO $~3_{03}-2_{02}$ line at 218.2 GHz (with 12" angular resolution). We determine the H2CO abundances using a detailed radiative transfer analysis and compare these results with PDR models that include either pure gas-phase chemistry or both gas-phase and grain surface chemistry. Results: The H2CO abundances ($\simeq 2-3 \times 10^{-10}$) with respect to H-nuclei are similar in the PDR and dense-core. In the dense-core the pure gas-phase chemistry model reproduces the observed H2CO abundance. Thus, surface processes do not contribute significantly to the gas-phase H2CO abundance in the core. In contrast, the formation of H2CO on the surface of dust grains and subsequent photo-desorption into the gas-phase are needed in the PDR to explain the observed gas-phase H2CO abundance, because the gas-phase chemistry alone does not produce enough H2CO. The assignments of different formation routes are strengthen by the different measured ortho-to-para ratio of H2CO: the dense-core displays the equilibrium value ($\sim3$) while the PDR displays an out-of-equilibrium value ($\sim2$). Conclusions: Photo-desorption of H2CO ices is an efficient mechanism to release a significant amount of gas-phase H2CO into the Horsehead PDR.