arXiv subjects

E. Herbst

Publications and source records attributed to E. Herbst.

65 records · Page 4Linked to original sources

arXiv2007

Gas-grain chemistry in cold interstellar cloud cores with a microscopic Monte Carlo approach to surface chemistry

AIM: We have recently developed a microscopic Monte Carlo approach to study surface chemistry on interstellar grains and the morphology of ice mantles. The method is designed to eliminate the problems inherent in the rate-equation formalism to surface chemistry. Here we report the first use of this method in a chemical model of cold interstellar cloud cores that includes both gas-phase and surface chemistry. The surface chemical network consists of a small number of diffusive reactions that can produce molecular oxygen, water, carbon dioxide, formaldehyde, methanol and assorted radicals. METHOD: The simulation is started by running a gas-phase model including accretion onto grains but no surface chemistry or evaporation. The starting surface consists of either flat or rough olivine. We introduce the surface chemistry of the three species H, O and CO in an iterative manner using our stochastic technique. Under the conditions of the simulation, only atomic hydrogen can evaporate to a significant extent. Although it has little effect on other gas-phase species, the evaporation of atomic hydrogen changes its gas-phase abundance, which in turn changes the flux of atomic hydrogen onto grains. The effect on the surface chemistry is treated until convergence occurs. We neglect all non-thermal desorptive processes. RESULTS: We determine the mantle abundances of assorted molecules as a function of time through 2x10^5 yr. Our method also allows determination of the abundance of each molecule in specific monolayers. The mantle results can be compared with observations of water, carbon dioxide, carbon monoxide, and methanol ices in the sources W33A and Elias 16. Other than a slight underproduction of mantle CO, our results are in very good agreement with observations.

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arXiv2007

Non-thermal desorption from interstellar dust grains via exothermic surface reactions

Aims: The gas-phase abundance of methanol in dark quiescent cores in the interstellar medium cannot be explained by gas-phase chemistry. In fact, the only possible synthesis of this species appears to be production on the surfaces of dust grains followed by desorption into the gas. Yet, evaporation is inefficient for heavy molecules such as methanol at the typical temperature of 10 K. It is necessary then to consider non-thermal mechanisms for desorption. But, if such mechanisms are considered for the production of methanol, they must be considered for all surface species. Methods: Our gas-grain network of reactions has been altered by the inclusion of a non-thermal desorption mechanism in which the exothermicity of surface addition reactions is utilized to break the bond between the product species and the surface. Our estimated rate for this process derives from a simple version of classical unimolecular rate theory with a variable parameter only loosely contrained by theoretical work. Results: Our results show that the chemistry of dark clouds is altered slightly at times up to 10^6 yr, mainly by the enhancement in the gas-phase abundances of hydrogen-rich species such as methanol that are formed on grain surfaces. At later times, however, there is a rather strong change. Instead of the continuing accretion of most gas-phase species onto dust particles, a steady-state is reached for both gas-phase and grain-surface species, with significant abundances for the former. Nevertheless, most of the carbon is contained in an undetermined assortment of heavy surface hydrocarbons. Conclusions: The desorption mechanism discussed here will be better constrained by observational data on pre-stellar cores, where a significant accretion of species such as CO has already occurred.

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arXiv2006

Formation of methyl formate and other organic species in the warm-up phase of hot molecular cores

Aims: The production of saturated organic molecules in hot cores and corinos is not well understood. The standard approach is to assume that, as temperatures heat up during star formation, methanol and other species evaporate from grain surfaces and undergo a warm gas-phase chemistry at 100 K or greater to produce species such as methyl formate, dimethyl ether, and others. But a series of laboratory results shows that protonated ions, typical precursors to final products in ion-molecule schemes, tend to fragment upon dissociative recombination with electrons rather than just ejecting a hydrogen atom. Moreover, the specific proposed reaction to produce protonated methyl formate is now known not to occur at all. Methods: We utilize a gas-grain chemical network to probe the chemistry of the relatively ignored stage of hot core evolution during which the protostar switches on and the temperature of the surrounding gas and dust rises from 10 K to over 100 K. During this stage, surface chemistry involving heavy radicals becomes more important as surface hydrogen atoms tend to evaporate rather than react. Results: Our results show that complex species such as methyl formate, formic acid, and dimethyl ether can be produced in large abundance during the protostellar switch-on phase, but that both grain-surface and gas-phase processes help to produce most species. The longer the timescale for protostellar switch-on, the more important the surface processes.

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arXiv2006

Extreme Deuteration and Hot Corinos: the Earliest Chemical Signatures of Low-Mass Star Formation

Low-mass protostars form from condensations inside molecular clouds when gravity overwhelms thermal and magnetic supporting forces. The first phases of the formation of a solar-type star are characterized by dramatic changes not only in the physical structure but also in the chemical composition. Since PPIV (e.g., Langer et al.), exciting new developments have occurred in our understanding of the processes driving this chemical evolution. These developments include two new discoveries : 1) extremely enhanced molecular deuteration, which is caused by the freeze-out of heavy-element-bearing molecules onto grain mantles during the Prestellar Core and Class 0 source phases; and 2) hot corinos, which are warm and dense regions at the center of Class 0 source envelopes and which are characterized by a multitude of complex organic molecules. In this chapter we will review these two new topics, and will show how they contribute to our understanding of the first phases of solar-type stars.

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arXiv2003

First detection of triply-deuterated methanol

We report the first detection of triply-deuterated methanol, with 12 observed transitions, towards the low-mass protostar IRAS 16293-2422, as well as multifrequency observations of 13CH3OH, used to derive the column density of the main isotopomer CH3OH. The derived fractionation ratio [CD3OH]/[CH3OH] averaged on a 10'' beam is 1.4%. Together with previous CH2DOH and CHD2OH observations, the present CD3OH observations are consistent with a formation of methanol on grain surfaces, if the atomic D/H ratio is 0.1 to 0.3 in the accreting gas. Such a high atomic ratio can be reached in the frame of gas-phase chemical models including all deuterated isotopomers of H3+.

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arXiv2003

Deuterium fractionation on interstellar grains studied with the direct master equation approach

We have studied deuterium fractionation on interstellar grains with the use of an exact method known as the direct master equation approach. We consider conditions pertinent to dense clouds at late times when the hydrogen is mostly in molecular form and a large portion of the gas-phase carbon has already been converted to carbon monoxide. Hydrogen, oxygen and deuterium atoms, as well as CO molecules, are allowed to accrete on to dust particles and react there to produce various stable molecules. The surface abundances, as well as the abundance ratios between deuterated and normal isotopomers, are compared with those calculated with the Monte Carlo approach. We find that the agreement between the Monte Carlo and the direct master equation methods can be made as close as desired. Compared with previous examples of the use of the direct master equation approach, our present method is much more efficient. It should now be possible to run large-scale gas-grain models in which the diffusive dust chemistry is handled `exactly'.

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arXiv2003

On the master equation approach to diffusive grain-surface chemistry: the H, O, CO system

We have used the master equation approach to study a moderately complex network of diffusive reactions occurring on the surfaces of interstellar dust particles. This network is meant to apply to dense clouds in which a large portion of the gas-phase carbon has already been converted to carbon monoxide. Hydrogen atoms, oxygen atoms, and CO molecules are allowed to accrete onto dust particles and their chemistry is followed. The stable molecules produced are oxygen, hydrogen, water, carbon dioxide (CO2), formaldehyde (H2CO), and methanol (CH3OH). The surface abundances calculated via the master equation approach are in good agreement with those obtained via a Monte Carlo method but can differ considerably from those obtained with standard rate equations.

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arXiv2002

Detection of doubly-deuterated methanol in the solar-type protostar IRAS16293-2422

We report the first detection of doubly-deuterated methanol (CHD2OH), as well as firm detections of the two singly-deuterated isotopomers of methanol (CH2DOH and CH3OD), towards the solar-type protostar IRAS16293-2422. From the present multifrequency observations, we derive the following abundance ratios: [CHD2OH]/[CH3OH] = 0.2 +/- 0.1, [CH2DOH]/[CH3OH] = 0.9 +/- 0.3, [CH3OD]/[CH3OH] = 0.04 +/- 0.02. The total abundance of the deuterated forms of methanol is greater than that of its normal hydrogenated counterpart in the circumstellar material of IRAS16293-2422, a circumstance not previously encountered. Formaldehyde, which is thought to be the chemical precursor of methanol, possesses a much lower fraction of deuterated isotopomers (~ 20%) with respect to the main isotopic form in IRAS16293-2422. The observed fractionation of methanol and formaldehyde provides a severe challenge to both gas-phase and grain-surface models of deuteration. Two examples of the latter model are roughly in agreement with our observations of CHD2OH and CH2DOH if the accreting gas has a large (0.2-0.3) atomic D/H ratio. However, no gas-phase model predicts such a high atomic D/H ratio, and hence some key ingredient seems to be missing.

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arXiv2002

Two-dimensional Distributions and Column Densities of Gaseous Molecules in Protoplanetary Disks II

We have investigated the two-dimensional (R,Z) distribution of deuterated molecular species in circumstellar disks around young stellar objects. The abundance ratios between singly deuterated and normal molecules (``D/H ratios'') in disks evolve in a similar way as in molecular clouds. Fractionation is caused by rapid exchange reactions that are exothermic because of energy differences between deuterated and normal species. In the midplane region, where molecules are heavily depleted onto grain surfaces, the D/H ratios of gaseous molecules are higher than at larger heights. The D/H ratios for the vertical column densities of NH3, H2O, and HCO+ are sensitive to the temperature, and decrease significantly with decreasing radial distance for R < 300 AU. The analogous D/H ratios for CH4 and H2CO, on the other hand, are not very sensitive to the temperature in the range (T=10-50 K) we are concerned with, and do not decrease with decreasing R at R > 50 AU. The D/H column-density ratios also depend on disk mass. In a disk with a larger mass, the ratios of deuterated species to normal species are higher, because of heavier depletion of molecules onto grains. In the second part of the paper, we report molecular column densities for disks embedded in ambient cloud gas. Our results suggest that CN and HCO+ can be tracers of gaseous disks, especially if the central object is a strong X-ray source. Our results also suggest that the radial distributions of CN, C2H, HCN, and H2CO may vary among disks depending on the X-ray luminosity of the central star.

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arXiv2002

Warm Molecular Layers in Protoplanetary Disks

We have investigated molecular distributions in protoplanetary disks, adopting a disk model with a temperature gradient in the vertical direction. The model produces sufficiently high abundances of gaseous CO and HCO+ to account for line observations of T Tauri stars using a sticking probability of unity and without assuming any non-thermal desorption. In regions of radius R > 10 AU, with which we are concerned, the temperature increases with increasing height from the midplane. In a warm intermediate layer, there are significant amounts of gaseous molecules owing to thermal desorption and efficient shielding of ultraviolet radiation by the flared disk. The column densities of HCN, CN, CS, H2CO, HNC and HCO+ obtained from our model are in good agreement with the observations of DM Tau, but are smaller than those of LkCa15. Molecular line profiles from our disk models are calculated using a 2-dimensional non-local-thermal-equilibrium (NLTE) molecular-line radiative transfer code for a direct comparison with observations. Deuterated species are included in our chemical model. The molecular D/H ratios in the model are in reasonable agreement with those observed in protoplanetary disks.

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arXiv2002

Molecular Evolution in Collapsing Prestellar Cores

We have investigated the evolution and distribution of molecules in collapsing prestellar cores via numerical chemical models, adopting the Larson-Penston solution and its delayed analogues to study collapse. Molecular abundances and distributions in a collapsing core are determined by the balance among the dynamical, chemical and adsorption time scales. When the central density n_H of a prestellar core with the Larson-Penston flow rises to 3 10^6 cm^{-3}, the CCS and CO column densities are calculated to show central holes of radius 7000 AU and 4000 AU, respectively, while the column density of N2H+ is centrally peaked. These predictions are consistent with observations of L1544. If the dynamical time scale of the core is larger than that of the Larson-Penston solution owing to magnetic fields, rotation, or turbulence, the column densities of CO and CCS are smaller, and their holes are larger than in the Larson-Penston core with the same central gas density. On the other hand, N2H+ and NH3 are more abundant in the more slowly collapsing core. Therefore, molecular distributions can probe the collapse time scale of prestellar cores. Deuterium fractionation has also been studied via numerical calculations. The deuterium fraction in molecules increases as a core evolves and molecular depletion onto grains proceeds. When the central density of the core is n_H=3 10^6 cm^{-3}, the ratio DCO+/HCO+ at the center is in the range 0.06-0.27, depending on the collapse time scale and adsorption energy; this range is in reasonable agreement with the observed value in L1544.

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