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Gianfranco Vidali

Publications and source records attributed to Gianfranco Vidali.

At least 19 recordsLinked to original sources
arXiv2023

New measurement of the diffusion of carbon dioxide on non-porous amorphous solid water

The diffusion of molecules on interstellar grain surfaces is one of the most important driving forces for the molecular complexity in the interstellar medium. Due to the lack of laboratory measurements, astrochemical modeling of grain surface processes usually assumes a constant ratio between the diffusion energy barrier and the desorption energy. This over-simplification inevitably causes large uncertainty in model predictions. We present a new measurement of the diffusion of CO$_2$ molecules on the surface of non-porous amorphous solid water (np-ASW), an analog of the ice mantle that covers cosmic dust grains. A small coverage of CO$_2$ was deposited onto an np-ASW surface at 40~K, the subsequent warming of the ice activated the diffusion of CO$_2$ molecules, and a transition from isolated CO$_2$ to CO$_2$ clusters was seen in the infrared spectra. To obtain the diffusion energy barrier and pre-exponential factor simultaneously, a set of isothermal experiments were carried out. The values for the diffusion energy barrier and pre-exponential factor were found to be $1300\pm110$~K and $10^{7.6\pm0.8}$~s$^{-1}$. A comparison with prior laboratory measurements on diffusion is discussed.

astro-ph.IM↗
arXiv2022

Ammonia, carbon dioxide and the non-detection of the 2152 cm$^{-1}$ CO band

CO is one of the most abundant ice components on interstellar dust grains. When it is mixed with amorphous solid water (ASW) or located on its surface, an absorption band of CO at 2152 cm$^{-1}$ is always present in laboratory measurements. This spectral feature is attributed to the interaction of CO with dangling-OH bonds (dOH) in ASW. However, this band is absent in observational spectra of interstellar ices. This raises the question whether CO forms a relatively pure layer on top of ASW or is in close contact with ASW, but not via dangling bonds. We aim to determine whether the incorporation of NH$_3$ or CO$_2$ into ASW blocks the dOH and therefore reduces the 2152 cm$^{-1}$ band. We performed laboratory experiments to simulate the layered structure of the ice mantle, that is, we grew CO ice on top of 1) pure ASW, 2) NH$_3$:H$_2$O=10:100 mixed ice, and 3) CO$_2$:H$_2$O=20:100 mixed ice. Infrared spectra were measured to quantify the strength of the 2152 cm$^{-1}$ band. In addition, a second set of experiments were performed to determine how the incorporation of NH$_3$ into ASW affects the dOH band. We found that annealing the ice reduces the 2152 cm$^{-1}$ band and that NH$_3$ blocks the dOH on ASW surface and therefore reduces the 2152 cm$^{-1}$ band more effectively than CO$_2$. We suggest that this difference between NH$_3$ and CO$_2$ can be ascribed to the polarity of the guest molecule (NH$_3$ is a polar species, whereas CO$_2$ is apolar). The polarity implies that the formation of an H-bond between the N atom of ammonia and the dOH is a barrier-less reaction. We also determined the pore surface area of the ice mixtures as a function of the annealing temperature, and found that the nondetection of 2152 cm$^{-1}$ band does not necessarily exclude the possibility of a porous ice mantle.

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arXiv2019

The Effective Surface Area of Amorphous Solid Water Measured by the Infrared Absorption of Carbon Monoxide

The need to characterize ices coating dust grains in dense interstellar clouds arises from the importance of ice morphology in facilitating the diffusion and storage of radicals and reaction products in ices, a well-known place for the formation of complex molecules. Yet, there is considerable uncertainty about the structure of ISM ices, their ability to store volatiles and under what conditions. We measured the infrared absorption spectra of CO on the pore surface of porous amorphous solid water (ASW), and quantified the effective pore surface area of ASW. Additionally, we present results obtained from a Monte Carlo model of ASW in which the morphology of the ice is directly visualized and quantified. We found that 200 ML of ASW annealed to 20 K has a total pore surface area that is equivalent to 46 ML. This surface area decreases linearly with temperature to about 120 K. We also found that (1) dangling OH bonds only exist on the surface of pores; (2) almost all of the pores in the ASW are connected to the vacuum--ice interface, and are accessible for adsorption of volatiles from the gas phase; there are few closed cavities inside ASW at least up to a thickness of 200 ML; (3) the total pore surface area is proportional to the total 3-coordinated water molecules in the ASW in the temperature range 60--120 K. We also discuss the implications on the structure of ASW and surface reactions in the ice mantle in dense clouds.

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arXiv2018

The $^{12}$CO$_2$ and $^{13}$CO$_2$ Absorption Bands as Tracers of the Thermal History of Interstellar Icy Grain Mantles

Analyses of infrared signatures of CO$_2$ in water dominated ices in the ISM can give information on the physical state of CO$_2$ in icy grains and on the thermal history of the ices themselves. In many sources, CO$_2$ was found in the `pure' crystalline form, as signatured by the splitting in the bending mode absorption profile. To a large extent, pure CO$_2$ is likely to have formed from segregation of CO$_2$ from a CO$_2$:H$_2$O mixture during thermal processing. Previous laboratory studies quantified the temperature dependence of segregation, but no systematic measurement of the concentration dependence of segregation is available. In this study, we measured both the temperature dependence and concentration dependence of CO$_2$ segregation in CO$_2$:H$_2$O mixtures, and found that no pure crystalline CO$_2$ forms if the CO$_2$:H$_2$O ratio is less than 23%. Therefore the segregation of CO$_2$ is not always a good thermal tracer of the ice mantle. We found that the position and width of the broad component of the asymmetric stretching vibrational mode of $^{13}$CO$_2$ change linearly with the temperature of CO$_2$:H$_2$O mixtures, but are insensitive to the concentration of CO$_2$. We recommend using this mode, which will be observable towards low mass protostellar envelopes and dense clouds with the James Webb Space Telescope, to trace the thermal history of the ice mantle, especially when segregated CO$_2$ is unavailable. We used the laboratory measured $^{13}$CO$_2$ profile to analyze the ISO-SWS observations of ice mantles towards Young Stellar Objects, and the astrophysical implications are discussed.

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arXiv2018

Measurements of diffusion of volatiles in amorphous solid water: application to interstellar medium environments

The diffusion of atoms and molecules in ices covering dust grains in dense clouds in interstellar space is an important but poorly characterized step in the formation of complex molecules in space. Here we report the measurement of diffusion of simple molecules in amorphous solid water (ASW), an analog of interstellar ices, which are amorphous and made mostly of water molecules. The new approach that we used relies on measuring in situ the change in band strength and position of mid-infrared features of OH dangling bonds as molecules move through pores and channels of ASW. We obtained the Arrhenius pre-exponents and activation energies for diffusion of CO, O$_2$, N$_2$, CH$_4$, and Ar in ASW. The diffusion energy barrier of H$_2$ and D$_2$ were also measured, but only upper limits were obtained. These values constitute the first comprehensive set of diffusion parameters of simple molecules on the pore surface of ASW, and can be used in simulations of the chemical evolution of ISM environments, thus replacing unsupported estimates. We also present a set of argon temperature programmed desorption experiments to determine the desorption energy distribution of argon on non-porous ASW.

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arXiv2017

H$_2$ formation on interstellar dust grains: the viewpoints of theory, experiments, models and observations

Molecular hydrogen is the most abundant molecule in the universe. It is the first one to form and survive photo-dissociation in tenuous environments. Its formation involves catalytic reactions on the surface of interstellar grains. The micro-physics of the formation process has been investigated intensively in the last 20 years, in parallel of new astrophysical observational and modeling progresses. In the perspectives of the probable revolution brought by the future satellite JWST, this article has been written to present what we think we know about the H$_2$ formation in a variety of interstellar environments.

astro-ph.GA↗
arXiv2017

Mechanism of Atomic Hydrogen Addition Reactions on np-ASW

Hydrogen, being the most abundant element, is the driver of many if not most reactions occurring on interstellar dust grains. In hydrogen atom addition reactions, the rate is usually determined by the surface kinetics of the hydrogen atom instead of the other reaction partner. Three mechanisms exist to explain hydrogen addition reactions on surfaces: Langmuir-Hinshelwood, Eley-Rideal, and hot-atom. In gas-grain models, which mechanism is assumed greatly affects the simulation results. In this work, we quantify the temperature dependence of the rates of atomic hydrogen addition reactions by studying the reaction of H+O$_3$$\rightarrow$O$_2$+OH on the surface of a film of non-porous amorphous solid water (np-ASW) in the temperature range from 10 K to 50 K. The reaction rate is found to be temperature independent. This disagrees with the results of simulations with a network of rate equations that assume Langmuir-Hinshelwood mechanism through either thermal diffusion or tunneling diffusion; the reaction rates assuming such mechanism possesses a strong temperature dependence, either explicitly or implicitly, that is not seen experimentally. We suggest that the Eley-Rideal and/or hot-atom mechanism play a key role in hydrogen atom addition reactions, and should be included in gas-grain models. We also suggest that our newly developed time-resolved reactive scattering can be utilized to measure the chemical desorption efficiency in grain surface reactions.

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arXiv2017

Characterization of thin film CO$_2$ ice through the infrared $ν_1+ν_3$ combination mode

Carbon dioxide is abundant in ice mantles of dust grains; some is found in the pure crystalline form as inferred from the double peak splitting of the bending profile at about 650 cm$^{-1}$. To study how CO$_2$ segregates into the pure form from water-rich mixtures of ice mantles and how it then crystallizes, we used Reflection Absorption InfraRed Spectroscopy (RAIRS) to study the structural change of pure CO$_2$ ice as a function of both ice thickness and temperature. We found that the $ν_1+ν_3$ combination mode absorption profile at 3708~cm$^{-1}$ provides an excellent probe to quantify the degree of crystallinity in CO$_2$ ice. We also found that between 20 and 30~K, there is an ordering transition that we attribute to reorientation of CO$_2$ molecules, while the diffusion of CO$_2$ becomes significant at much higher temperatures. In the formation of pure crystalline CO$_2$ in ISM ices, the rate limiting process is the diffusion/segregation of CO$_2$ molecules in the ice instead of the phase transition from amorphous to crystalline after clusters/islands of CO$_2$ are formed.

astro-ph.IM↗
arXiv2016

Diffusion and Clustering of Carbon Dioxide on non-porous Amorphous Solid Water

Observations by ISO and Spitzer towards young stellar objects (YSOs) showed that CO$_2$ segregates in the icy mantles covering dust grains. Thermal processing of ice mixture was proposed as responsible for the segregation. Although several laboratory studied thermally induced segregation, a satisfying quantification is still missing. We propose that the diffusion of CO$_2$ along pores inside water ice is the key to quantify segregation. We combined Temperature Programmed Desorption (TPD) and Reflection Absorption InfraRed Spectroscopy (RAIRS) to study how CO$_2$ molecules interact on a non-porous amorphous solid water (np-ASW) surface. We found that CO$_2$ diffuses significantly on a np-ASW surface above 65~K and clusters are formed at well below one monolayer. A simple rate equation simulation finds that the diffusion energy barrier of CO$_2$ on np-ASW is 2150$\pm$50 K, assuming a diffusion pre-exponential factor of 10$^{12}$ s$^{-1}$. This energy should also apply to the diffusion of CO$_2$ on wall of pores. The binding energy of CO$_2$ from CO$_2$ clusters and CO$_2$ from H$_2$O ice have been found to be $2415\pm20$ and $2250\pm20$~K, respectively, assuming the same prefactor for desorption. CO$_2$-CO$_2$ interaction is stronger than CO$_2$-H$_2$O interaction, in agreement with the experimental finding that CO$_2$ does not wet np-ASW surface. For comparison, we carried out similar experiments with CO on np-ASW, and found that the CO-CO interaction is always weaker than CO-H$_2$O. As a result, CO wets np-ASW surface. This study should be of help to uncover the thermal history of CO$_2$ on the icy mantles of dust grains.

astro-ph.GA↗
arXiv2016

Sticking of molecules on non-porous amorphous water ice

Accurate modeling of physical and chemical processes in the interstellar medium requires detailed knowledge of how atoms and molecule adsorb on dust grains. However, the sticking coefficient, a number between 0 and 1 that measures the first step in the interaction of a particle with a surface, is usually assumed in simulations of ISM environments to be either 0.5 or 1. Here we report on the determination of the sticking coefficient of H$_2$, D$_2$, N$_2$, O$_2$, CO, CH$_4$, and CO$_2$ on non-porous amorphous solid water (np-ASW). The sticking coefficient was measured over a wide range of surface temperatures using a highly collimated molecular beam. We showed that the standard way of measuring the sticking coefficient --- the King-Wells method --- leads to the underestimation of trapping events in which there is incomplete energy accommodation of the molecule on the surface. Surface scattering experiments with the use of a pulsed molecular beam are used instead to measure the sticking coefficient. Based on the values of the measured sticking coefficient we suggest a useful general formula of the sticking coefficient as a function of grain temperature and molecule-surface binding energy. We use this formula in a simulation of ISM gas-grain chemistry to find the effect of sticking on the abundance of key molecules both on grains and in the gas-phase.

astro-ph.IM↗
arXiv2016

Binding Energy of Molecules on Water Ice: Laboratory Measurements and Modeling

We measured the binding energy of N$_2$, CO, O$_2$, CH$_4$, and CO$_2$ on non-porous (compact) amorphous solid water (np-ASW), of N$_2$ and CO on porous amorphous solid water (p-ASW), and of NH$_3$ on crystalline water ice. We were able to measure binding energies down to a fraction of 1\% of a layer, thus making these measurements more appropriate for astrochemistry than the existing values. We found that CO$_2$ forms clusters on np-ASW surface even at very low coverages. The binding energies of N$_2$, CO, O$_2$, and CH$_4$ decrease with coverage in the submonolayer regime. Their values at the low coverage limit are much higher than what is commonly used in gas-grain models. An empirical formula was used to describe the coverage dependence of the binding energies. We used the newly determined binding energy distributions in a simulation of gas-grain chemistry for cold cloud and hot core models. We found that owing to the higher value of desorption energy in the sub-monlayer regime a fraction of all these ices stays much longer and up to higher temperature on the grain surface compared to the single value energies currently used in the astrochemical models.

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arXiv2015

A New Determination of the Binding Energy of Atomic Oxygen on Dust Grain Surfaces: Experimental Results and Simulations

The energy to desorb atomic oxygen from an interstellar dust grain surface, $E_{\rm des}$, is an important controlling parameter in gas-grain models; its value impacts the temperature range over which oxygen resides on a dust grain. However, no prior measurement has been done of the desorption energy. We report the first direct measurement of $E_{\rm des}$ for atomic oxygen from dust grain analogs. The values of $E_{\rm des}$ are $1660\pm 60$~K and $1850\pm 90$~K for porous amorphous water ice and for a bare amorphous silicate film, respectively, or about twice the value previously adopted in simulations of the chemical evolution of a cloud. We use the new values to study oxygen chemistry as a function of depth in a molecular cloud. For $n=10^4$ cm$^{-3}$ and $G_0$=10$^2$ ($G_0$=1 is the average local interstellar radiation field), the main result of the adoption of the higher oxygen binding energy is that H$_2$O can form on grains at lower visual extinction $A_{\rm V}$, closer to the cloud surface. A higher binding energy of O results in more formation of OH and H$_2$O on grains, which are subsequently desorbed by FUV radiation, with consequences for gas-phase chemistry. For higher values of $n$ and $G_0$, the higher binding energy can lead to a large increase in the column of H$_2$O but a decrease in the column of O$_2$.

astro-ph.GA↗
arXiv2015

Formation of hydroxylamine on dust grains via ammonia oxidation

The quest to detect prebiotic molecules in space, notably amino acids, requires an understanding of the chemistry involving nitrogen atoms. Hydroxylamine (NH$_2$OH) is considered a precursor to the amino acid glycine. Although not yet detected, NH$_2$OH is considered a likely target of detection with ALMA. We report on an experimental investigation of the formation of hydroxylamine on an amorphous silicate surface via the oxidation of ammonia. The experimental data are then fed into a simulation of the formation of NH$_2$OH in dense cloud conditions. On ices at 14 K and with a modest activation energy barrier, NH$_2$OH is found to be formed with an abundance that never falls below a factor 10 with respect to NH$_3$. Suggestions of conditions for future observations are provided.

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arXiv2012

Division XII / Commission 14 / Working Group Solids and Their Surfaces

The ISO and Spitzer space observatories yielded a treasure trove of data on dust and ices covering dust grains. Now Herschel, and soon SOFIA and ALMA, will provide unprecedented views of the molecular world of the interstellar medium (ISM). It is on dust grains that key ISM molecules, such as hydrogen, formaldehyde, methanol, and water are formed. As a result of these new observations, there is a great need to know more about the interaction processes of atoms and molecules with dust grains. (The Proceedings of the 2010 NASA Laboratory Astrophysics Workshop (http://www-cfadc.phy.ornl.gov/nasa_law/) give a good view of recent accomplishments in the study of atom/molecule - solid interactions as well as other aspects of laboratory astrophysics.)

astro-ph.SR↗
arXiv2010

Interaction of Atomic and Molecular Hydrogen with Tholin Surfaces at Low Temperatures

We study the interaction of atomic and molecular hydrogen with a surface of tholin, a man-made polymer considered to be an analogue of aerosol particles present in Titan's atmosphere, using thermal programmed desorption at low temperatures below 30 K. The results are fitted and analyzed using a fine-grained rate equation model that describes the diffusion, reaction and desorption processes. We obtain the energy barriers for diffusion and desorption of atomic and molecular hydrogen. These barriers are found to be in the range of 30 to 60 meV, indicating that atom/molecule-surface interactions in this temperature range are dominated by weak adsorption forces. The implications of these results for the understanding of the atmospheric chemistry of Titan are discussed.

astro-ph.EP↗
arXiv2007

Formation of molecular hydrogen on amorphous silicate surfaces

Experimental results on the formation of molecular hydrogen on amorphous silicate surfaces are presented and analyzed using a rate equation model. The energy barriers for the relevant diffusion and desorption processes are obtained. They turn out to be significantly higher than those obtained for polycrystalline silicates, demonstrating the importance of grain morphology. Using these barriers we evaluate the efficiency of molecular hydrogen formation on amorphous silicate grains under interstellar conditions. It is found that unlike polycrystalline silicates, amorphous silicate grains are efficient catalysts of H_2 formation in diffuse interstellar clouds.

astro-ph↗
arXiv2007

Molecular Hydrogen Formation on Amorphous Silicates Under Interstellar Conditions

Experimental results on the formation of molecular hydrogen on amorphous silicate surfaces are presented for the first time and analyzed using a rate equation model. The energy barriers for the relevant diffusion and desorption processes are obtained. They turn out to be significantly higher than those obtained earlier for polycrystalline silicates, demonstrating the importance of grain morphology. Using these barriers we evaluate the efficiency of molecular hydrogen formation on amorphous silicate grains under interstellar conditions. It is found that unlike polycrystalline silicates, amorphous silicate grains are efficient catalysts of H$_{2}$ formation within a temperature range which is relevant to diffuse interstellar clouds. The results also indicate that the hydrogen molecules are thermalized with the surface and desorb with low kinetic energy. Thus, they are unlikely to occupy highly excited states.

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