arXiv subjects

Valentine Wakelam

Publications and source records attributed to Valentine Wakelam.

At least 73 records · Page 4Linked to original sources

arXiv2013

Water in Protoplanetary Disks: Deuteration and Turbulent Mixing

We investigate water and deuterated water chemistry in turbulent protoplanetary disks. Chemical rate equations are solved with the diffusion term, mimicking turbulent mixing in vertical direction. Water near the midplane is transported to the disk atmosphere by turbulence and destroyed by photoreactions to produce atomic oxygen, while the atomic oxygen is transported to the midplane and reforms water and/or other molecules. We find that this cycle significantly decreases column densities of water ice at r < 30 AU, where dust temperatures are too high to reform water ice effectively. The radial extent of such region depends on the desorption energy of atomic hydrogen. Our model indicates that water ice could be deficient even outside the sublimation radius. Outside this radius, the cycle decreases the D/H ratio of water ice from 2x10^-2, which is set by the collapsing core model, to 10^-4-10^-2 in 10^6 yr, without significantly decreasing the water ice column density. The resultant D/H ratios depend on the strength of mixing and the radial distance from the central star. Our finding suggests that the D/H ratio of cometary water (10^-3-10^-4) could be established (i.e. cometary water could be formed) in the solar nebula, even if the D/H ratio of water ice delivered to the disk was very high (10^-2).

astro-ph.GA↗

arXiv2013

Astrochemistry: Synthesis and Modelling

We discuss models that astrochemists have developed to study the chemical composition of the interstellar medium. These models aim at computing the evolution of the chemical composition of a mixture of gas and dust under as- trophysical conditions. These conditions, as well as the geometry and the physical dynamics, have to be adapted to the objects being studied because different classes of objects have very different characteristics (temperatures, densities, UV radia- tion fields, geometry, history etc); e.g., proto-planetary disks do not have the same characteristics as protostellar envelopes. Chemical models are being improved continually thanks to comparisons with observations but also thanks to laboratory and theoretical work in which the individual processes are studied.

astro-ph.GA↗

arXiv2013

Survival of interstellar molecules to prestellar dense core collapse and early phases of disk formation

An outstanding question of astrobiology is the link between the chemical composition of planets, comets, and other solar system bodies and the molecules formed in the interstellar medium. Understanding the chemical and physical evolution of the matter leading to the formation of protoplanetary disks is an important step for this. We provide some new clues to this long-standing problem using three-dimensional chemical simulations of the early phases of disk formation: we interfaced the full gas-grain chemical model Nautilus with the radiation-magnetohydrodynamic model RAMSES, for different configurations and intensities of magnetic field. Our results show that the chemical content (gas and ices) is globally conserved during the collapsing process, from the parent molecular cloud to the young disk surrounding the first Larson core. A qualitative comparison with cometary composition suggests that comets are constituted of different phases, some molecules being direct tracers of interstellar chemistry, while others, including complex molecules, seem to have been formed in disks, where higher densities and temperatures allow for an active grain surface chemistry. The latter phase, and its connection with the formation of the first Larson core, remains to be modeled.

astro-ph.SR↗

arXiv2013

Low temperature rate constants for the N(4S) + CH(X2Πr) reaction. Implications for N2 formation cycles in dense interstellar clouds

Rate constants for the potentially important interstellar N(4S) + CH(X2Πr) reaction have been measured in a continuous supersonic flow reactor over the range 56 K < T < 296 K using the relative rate technique employing both the N(4S) + OH(X2Πi) and N(4S) + CN(X2Σ+) reactions as references. Excess concentrations of atomic nitrogen were produced by the microwave discharge method upstream of the Laval nozzle and CH and OH radicals were created by the in-situ pulsed laser photolysis of suitable precursor molecules. In parallel, quantum dynamics calculations of the title reaction have been performed based on accurate global potential energy surfaces for the 13A' and 13A" states of HCN and HNC, brought about through a hierarchical construction scheme. Both adiabatic potential energy surfaces are barrierless, each one having two deep potential wells suggesting that this reaction is dominated by a complex-forming mechanism. The experimental and theoretical work are inexcellent agreement, predicting a positive temperature dependence of the rate constant, in contrast to earlier experimental work at low temperature. The effects of the new low temperature rate constants on interstellar N2 formation are tested using a dense cloud model, yielding N2 abundances 10-20 % lower than previously predicted.

astro-ph.GA↗

arXiv2012

From Prestellar to Protostellar Cores II. Time Dependence and Deuterium Fractionation

We investigate the molecular evolution and D/H abundance ratios that develop as star formation proceeds from a dense-cloud core to a protostellar core, by solving a gas-grain reaction network applied to a 1-D radiative hydrodynamic model with infalling fluid parcels. Spatial distributions of gas and ice-mantle species are calculated at the first-core stage, and at times after the birth of a protostar. Gas-phase methanol and methane are more abundant than CO at radii $r\lesssim 100$ AU in the first-core stage, but gradually decrease with time, while abundances of larger organic species increase. The warm-up phase, when complex organic molecules are efficiently formed, is longer-lived for those fluid parcels in-falling at later stages. The formation of unsaturated carbon chains (warm carbon-chain chemistry) is also more effective in later stages; C$^+$, which reacts with CH$_4$ to form carbon chains, increases in abundance as the envelope density decreases. The large organic molecules and carbon chains are strongly deuterated, mainly due to high D/H ratios in the parent molecules, determined in the cold phase. We also extend our model to simulate simply the chemistry in circumstellar disks, by suspending the 1-D infall of a fluid parcel at constant disk radii. The species CH$_3$OCH$_3$ and HCOOCH$_3$ increase in abundance in $10^4-10^5$ yr at the fixed warm temperature; both also have high D/H ratios.

astro-ph.GA↗

arXiv2012

Chemistry in the First Hydrostatic Core Stage By Adopting Three-Dimensional Radiation Hydrodynamic Simulations

We investigate molecular evolution from a molecular cloud core to a first hydrostatic core in three spatial dimensions. We perform a radiation hydrodynamic simulation in order to trace fluid parcels, in which molecular evolution is investigated, using a gas-phase and grain-surface chemical reaction network. We derive spatial distributions of molecular abundances and column densities in the core harboring the first core. We find that the total of gas and ice abundances of many species in a cold era (10 K) remain unaltered until the temperature reaches ~500 K. The gas abundances in the warm envelope and the outer layer of the first core (T < 500 K) are mainly determined via the sublimation of ice-mantle species. Above 500 K, the abundant molecules, such as H2CO, start to be destroyed, and simple molecules, such as CO, H2O and N2 are reformed. On the other hand, some molecules are effectively formed at high temperature; carbon-chains, such as C2H2 and cyanopolyynes, are formed at the temperature of >700 K. We also find that large organic molecules, such as CH3OH and HCOOCH3, are associated with the first core (r < 10 AU). Although the abundances of these molecules in the first core stage are comparable or less than in the protostellar stage (hot corino), reflecting the lower luminosity of the central object, their column densities in our model are comparable to the observed values toward the prototypical hot corino, IRAS 16293-2422. We propose that these large organic molecules can be good tracers of the first cores.

astro-ph.SR↗

arXiv2012

Elemental nitrogen partitioning in dense interstellar clouds

Many chemical models of dense interstellar clouds predict that the majority of gas-phase elemental nitrogen should be present as N2, with an abundance approximately five orders of magnitude less than that of hydrogen. As a homonuclear diatomic molecule, N2 is difficult to detect spectroscopically through infrared or millimetre-wavelength transitions so its abundance is often inferred indirectly through its reaction product N2H+. Two main formation mechanisms each involving two radical-radical reactions are the source of N2 in such environments. Here we report measurements of the low temperature rate constants for one of these processes, the N + CN reaction down to 56 K. The effect of the measured rate constants for this reaction and those recently determined for two other reactions implicated in N2 formation are tested using a gas-grain model employing a critically evaluated chemical network. We show that the amount of interstellar nitrogen present as N2 depends on the competition between its gas-phase formation and the depletion of atomic nitrogen onto grains. As the reactions controlling N2 formation are inefficient, we argue that N2 does not represent the main reservoir species for interstellar nitrogen. Instead, elevated abundances of more labile forms of nitrogen such as NH3 should be present on interstellar ices, promoting the eventual formation of nitrogen-bearing organic molecules.

astro-ph.GA↗

arXiv2012

Review of OCS gas-phase reactions in dark cloud chemical models

The association reaction S + CO {\to} OCS + hnu has been identified as being particularly important for the prediction of gas-phase OCS abundances by chemical models of dark clouds. We performed detailed ab-initio calculations for this process in addition to undertaking an extensive review of the neutral-neutral reactions involving this species which might be important in such environments. The rate constant for this association reaction was estimated to be several orders of magnitude smaller than the one present in current astrochemical databases. The new rate for this reaction and the introduction of other processes, notably OH + CS {\to} OCS + H and C + OCS {\to} CO + CS, dramatically changes the OCS gas-phase abundance predicted by chemical models for dark clouds. The disagreement with observations in TMC-1 (CP) and L134N (N), suggests that OCS may be formed on grain surfaces as is the case for methanol. The observation of solid OCS on interstellar ices supports this hypothesis.

astro-ph.GA↗

arXiv2011

CID: Chemistry in disks VI.sulfur-bearing molecules in the protoplanetary disks surrounding LkCa15, MWC480, DM Tau, and GO Tau

We study the content in S-bearing molecules of protoplanetary disks around low-mass stars. We used the new IRAM 30-m receiver EMIR to perform simultaneous observations of the $1_{10}-1_{01}$ line of H$_2$S at 168.8 GHz and $2_{23}-1_{12}$ line of SO at 99.3 GHz. We compared the observational results with predictions coming from the astrochemical code NAUTILUS, which has been adapted to protoplanetary disks. The data were analyzed together with existing CS J=3-2 observations. We fail to detect the SO and H$_2$S lines, although CS is detected in LkCa15, DM\,Tau, and GO\,Tau but not in MWC\,480. However, our new upper limits are significantly better than previous ones and allow us to put some interesting constraints on the sulfur chemistry. Our best modeling of disks is obtained for a C/O ratio of 1.2, starting from initial cloud conditions of H density of $2\times 10^5$ cm$^{-3}$ and age of $10^6$ yr. The results agree with the CS data and are compatible with the SO upper limits, but fail to reproduce the H$_2$S upper limits. The predicted H$_2$S column densities are too high by at least one order of magnitude. H$_2$S may remain locked onto grain surfaces and react with other species, thereby preventing the desorption of H$_2$S.

astro-ph.SR↗

arXiv2009

S-bearing molecules in Massive Dense Cores

Chemical composition of the massive cores forming high-mass stars can put some constrains on the time scale of the massive star formation: sulphur chemistry is of specific interest due to its rapid evolution in warm gas and because the abundance of sulphur bearing species increases significantly with the temperature. Two mid-infrared quiet and two brighter massive cores are observed in various transitions (E_up up to 289K) of CS, OCS, H2S, SO, SO2 and of their isotopologues at mm wavelengths with the IRAM 30m and CSO telescopes. 1D modeling of the dust continuum is used to derive the density and temperature laws, which are then applied in the RATRAN code to model the observed line emission, and to derive the relative abundances of the molecules. All lines, except the highest energy SO2 transition, are detected. Infall (up to 2.9km/s) may be detected towards the core W43MM1. The inferred mass rate is 5.8-9.4 10^{-2} M_{\odot}/yr. We propose an evolutionary sequence of our sources (W43MM1-IRAS18264-1152-IRAS05358+3543-IRAS18162-2048), based on the SED analysis. The analysis of the variations in abundance ratios from source to source reveals that the SO and SO2 relative abundances increase with time, while CS and OCS decrease. Molecular ratios, such as [OCS/H2S], [CS/H2S], [SO/OCS], [SO2/OCS], [CS/SO] and [SO2/SO] may be good indicators of evolution depending on layers probed by the observed molecular transitions. Observations of molecular emission from warmer layers, hence involving higher upper energy levels are mandatory to include.

astro-ph.SR↗

arXiv2009

A sensitivity study of the neutral-neutral reactions C + C3 and C + C5 in cold dense interstellar clouds

Chemical networks used for models of interstellar clouds contain many reactions, some of them with poorly determined rate coefficients and/or products. In this work, we report a method for improving the predictions of molecular abundances using sensitivity methods and ab initio calculations. Based on the chemical network osu.2003, we used two different sensitivity methods to determine the most important reactions as a function of time for models of dense cold clouds. Of these reactions, we concentrated on those between C and C3 and between C and C5, both for their effect on specific important species such as CO and for their general effect on large numbers of species. We then used ab initio and kinetic methods to determine an improved rate coefficient for the former reaction and a new set of products, plus a slightly changed rate coefficient for the latter. Putting our new results in a pseudo-time-dependent model of cold dense clouds, we found that the abundances of many species are altered at early times, based on large changes in the abundances of CO and atomic C. We compared the effect of these new rate coefficients/products on the comparison with observed abundances and found that they shift the best agreement from 3e4 yr to (1-3)e5 yr.

astro-ph.GA↗

arXiv2008

Composition of Ices in Low-Mass Extrasolar Planets

We study the formation conditions of icy planetesimals in protoplanetary disks in order to determine the composition of ices in small and cold extrasolar planets. Assuming that ices are formed from hydrates, clathrates, and pure condensates, we calculate their mass fractions with respect to the total quantity of ices included in planetesimals, for a grid of disk models. We find that the composition of ices weakly depends on the adopted disk thermodynamic conditions, and is rather influenced by the initial composition of the gas phase. The use of a plausible range of molecular abundance ratios and the variation of the relative elemental carbon over oxygen ratio in the gas phase of protoplanetary disks, allow us to apply our model to a wide range of planetary systems. Our results can thus be used to constrain the icy/volatile phase composition of cold planets evidenced by microlensing surveys, hypothetical ocean-planets and carbon planets, which could be detected by Corot or Kepler.

astro-ph↗

arXiv2008

Polycylcic Aromatic Hydrocarbons (PAH's) in dense cloud chemistry

Virtually all detailed gas-phase models of the chemistry of dense interstellar clouds exclude polycyclic aromatic hydrocarbons (PAH's). This omission is unfortunate because from the few studies that have been done on the subject, it is known that the inclusion of PAH's can affect the gas-phase chemistry strongly. We have added PAH's to our network to determine the role they play in the chemistry of cold dense cores. In the models presented here, we include radiative attachment to form PAH-, mutual neutralization between PAH anions and small positively-charged ions, and photodetachment. We also test the sensitivity of our results to changes in the size and abundance of the PAH's. Our results confirm that the inclusion of PAH's changes many of the calculated abundances of smaller species considerably. In TMC-1, the general agreement with observations is significantly improved contrary to L134N. This may indicate a difference in PAH properties between the two regions. With the inclusion of PAH's in dense cloud chemistry, high-metal elemental abundances give a satisfactory agreement with observations. As a result, we do not need to decrease the observed elemental abundances of all metals and we do not need to vary the elemental C/O ratio in order to produce large abundances of carbon species in TMC-1 (CP).

astro-ph↗

arXiv2007

Molecular Evolution and Star Formation: From Prestellar Cores to Protostellar Cores

We investigate molecular evolution in a star-forming core that is initially a hydrostatic starless core and collapses to form a low-mass protostar. The results of a one-dimensional radiation-hydrodynamics calculation are adopted as a physical model of the core. We first derive radii at which CO and large organic species sublimate. CO sublimation in the central region starts shortly before the formation of the first hydrostatic core. When the protostar is born, the CO sublimation radius extends to 100 AU, and the region inside $\lesssim 10$ AU is hotter than 100 K, at which some large organic species evaporate. We calculate the temporal variation of physical parameters in infalling shells, in which the molecular evolution is solved using an updated gas-grain chemical model to derive the spatial distribution of molecules in a protostellar core. The shells pass through the warm region of $10 -100$ K in several $\times$ $10^4$ yr, and fall into the central star $\sim 100$ yr after they enter the region where $T \gtrsim 100$ K. We find that large organic species are formed mainly via grain-surface reactions at temperatures of $20 -40$ K and then desorbed into the gas-phase at their sublimation temperatures. Carbon-chain species can be formed by a combination of gas-phase reactions and grain-surface reactions following the sublimation of CH$_4$. Our model also predicts that CO$_2$ is more abundant in isolated cores, while gas-phase large organic species are more abundant in cores embedded in ambient clouds.

astro-ph↗

arXiv2006

Chemical sensitivity to the ratio of the cosmic-ray ionization rates of He and H2 in dense clouds

Aim: To determine whether or not gas-phase chemical models with homogeneous and time-independent physical conditions explain the many observed molecular abundances in astrophysical sources, it is crucial to estimate the uncertainties in the calculated abundances and compare them with the observed abundances and their uncertainties. Non linear amplification of the error and bifurcation may limit the applicability of chemical models. Here we study such effects on dense cloud chemistry. Method: Using a previously studied approach to uncertainties based on the representation of rate coefficient errors as log normal distributions, we attempted to apply our approach using as input a variety of different elemental abundances from those studied previously. In this approach, all rate coefficients are varied randomly within their log normal (Gaussian) distribution, and the time-dependent chemistry calculated anew many times so as to obtain good statistics for the uncertainties in the calculated abundances. Results: Starting with so-called ``high-metal'' elemental abundances, we found bimodal rather than Gaussian like distributions for the abundances of many species and traced these strange distributions to an extreme sensitivity of the system to changes in the ratio of the cosmic ray ionization rate zeta\_He for He and that for molecular hydrogen zeta\_H2. The sensitivity can be so extreme as to cause a region of bistability, which was subsequently found to be more extensive for another choice of elemental abundances. To the best of our knowledge, the bistable solutions found in this way are the same as found previously by other authors, but it is best to think of the ratio zeta\_He/zeta\_H2 as a control parameter perpendicular to the ''standard'' control parameter zeta/n\_H.

astro-ph↗

arXiv2006

The effect of uncertainties on chemical models of dark clouds

The gas-phase chemistry of dark clouds has been studied with a treatment of uncertainties caused both by errors in individual rate coefficients and uncertainties in physical conditions. Moreover, a sensitivity analysis has been employed to attempt to determine which reactions are most important in the chemistry of individual species. The degree of overlap between calculated errors in abundances and estimated observational errors has been used as an initial criterion for the goodness of the model and the determination of a best 'chemical' age of the source. For the well-studied sources L134N and TMC-1CP, best agreement is achieved at so-called "early times" ~10$^{5}$ yr, in agreement with previous calculations but here put on a firmer statistical foundation. A more detailed criterion for agreement, which takes into account the degree of disagreement, is also proposed. Poorly understood but critical classes of reactions are delineated, especially reactions between ions and polar neutrals. Such reactions will have to be understood better before the chemistry can be made more secure. Nevertheless, the level of agreement is low enough to indicate that a static picture of physical conditions without consideration of interactions with grain surfaces is inappropriate for a complete understanding of the chemistry.

astro-ph↗

arXiv2005

Modeling the ortho-to-para abundance ratio of cyclic C3H2 in cold dense cores

We report a detailed attempt to model the ortho-to-para abundance ratio of c-C3H2 so as to reproduce observed values in the cores of the well-known source TMC-1. According to observations, the ortho-to-para ratios vary, within large uncertainties, from a low of near unity to a high of approximately three depending on the core. We used the osu.2003 network of gas-phase chemical reactions augmented by reactions that specifically consider the formation, depletion, and interconversion of the ortho and para forms of the c-C3H2 and its precursor ion c-C3H3+. We investigated the sensitivity of the calculated ortho-to-para ratio for c-C3H2 to a large number of factors. For the less evolved cores C, CP, and D, we had no difficulty reproducing the observed ortho-to-para ratios of 1-2.

astro-ph↗

arXiv2005

Estimation and reduction of the uncertainties in chemical models: Application to hot core chemistry

It is not common to consider the role of uncertainties in the rate coefficients used in interstellar gas-phase chemical models. In this paper, we report a new method to determine both the uncertainties in calculated molecular abundances and their sensitivities to underlying uncertainties in the kinetic data utilized. The method is used in hot core models to determine if previous analyses of the age and the applicable cosmic-ray ionization rate are valid. We conclude that for young hot cores ($\le 10^4$ yr), the modeling uncertainties related to rate coefficients are reasonable so that comparisons with observations make sense. On the contrary, the modeling of older hot cores is characterized by strong uncertainties for some of the important species. In both cases, it is crucial to take into account these uncertainties to draw conclusions from the comparison of observations with chemical models.

astro-ph↗