Grain Surface Chemistry: Modified Models

The rate equation approach to the chemistry occurring on grain surfaces in interstellar clouds has been criticized for not taking the discrete nature of grains into account. Indeed, investigations of simple models show that results obtained from rate equations can be significantly different from results obtained by a Monte Carlo procedure. Some modifications of the rate equations have been proposed that have the effect of eliminating most of the differences with the Monte Carlo procedure for simplified models of interstellar clouds at temperatures of 10 K and slightly above. In this study we investigate the use of the modified rate equations in more realistic chemical models of dark interstellar clouds with complex gas-grain interactions. Our results show some discrepancies between the results of models with unmodified and modified rate equations; these discrepancies are highly dependent, however, on the initial form of hydrogen chosen. If the initial form is mainly molecular, at early stages of cloud evolution there are some significant differences in calculated molecular abundances on grains, but at late times the two sets of results tend to converge for the main components of the grain mantles. If the initial form is atomic hydrogen, there are essentially no differences in results between models based on the unmodified rate equations and those based on the modified rate equations, except for the abundances on grains of some minor complex molecules. Thus, the major results of previous gas-grain models of cold, dark interstellar clouds remain at least partially intact

Moment equations for chemical reactions on interstellar dust grains

While most chemical reactions in the interstellar medium take place in the gas phase, those occurring on the surfaces of dust grains play an essential role. Chemical models based on rate equations including both gas phase and grain surface reactions have been used in order to simulate the formation of chemical complexity in interstellar clouds. For reactions in the gas phase and on large grains, rate equations, which are highly efficient to simulate, are an ideal tool. However, for small grains under low flux, the typical number of atoms or molecules of certain reactive species on a grain may go down to order one or less. In this case the discrete nature of the opulations of reactive species as well as the fluctuations become dominant, thus the mean-field approximation on which the rate equations are based does not apply. Recently, a master equation approach, that provides a good description of chemical reactions on interstellar dust grains, was proposed. Here we present a related approach based on moment equations that can be obtained from the master equation. These equations describe the time evolution of the moments of the distribution of the population of the various chemical species on the grain. An advantage of this approach is the fact that the production rates of molecular species are expressed directly in terms of these moments. Here we use the moment equations to calculate the rate of molecular hydrogen formation on small grains. It is shown that the moment equation approach is efficient in this case in which only a single reactive specie is involved. The set of equations for the case of two species is presented and the difficulties in implementing this approach for complex reaction networks involving multiple species are discussed.Comment: 12 pages, submitted for publication in A&

NMA Survey of CO and HCN Emission from Nearby Active Galaxies

High resolution (a few arcseconds) observations of CO(1-0) and HCN(1-0) emission from nearby Seyfert galaxies have been conducted with the Nobeyama Millimeter Array. Based on the observed CO distributions and kinematics,we suggest that a small scale (a few 100 pc - a few kpc) distortion of the underlying potential seems to be necessary for Seyfert activity, although it is not a sufficient condition. We also find that the Toomre's Q values in the centers of Seyfert galaxies tend to be larger than unity, indicating the circumnuclear molecular gas disks around Seyfert nuclei would be gravitationally stable. The HCN/CO integrated intensity ratios (R_HCN/CO) range over an order of magnitude, from 0.086 to 0.6. The Seyfert galaxies with high R_HCN/CO may have an extended (r ~ 100 pc scale) envelope of obscuring material. The presence of kpc scale jet/ outflow might be also related to the extremely high R_HCN/CO.Comment: To appear in the Proceedings of the 3rd Cologne-Zermatt Symposium, ``The Physics and Chemistry of the Interstellar Medium'

A Unified Monte Carlo Treatment of Gas-Grain Chemistry for Large Reaction Networks. I. Testing Validity of Rate Equations in Molecular Clouds

In this study we demonstrate for the first time that the unified Monte Carlo approach can be applied to model gas-grain chemistry in large reaction networks. Specifically, we build a time-dependent gas-grain chemical model of the interstellar medium, involving about 6000 gas-phase and 200 grain surface reactions. This model is used to test the validity of the standard and modified rate equation methods in models of dense and translucent molecular clouds and to specify under which conditions the use of the stochastic approach is desirable. We found that at temperatures 25--30 K gas-phase abundances of H$_2$O, NH$_3$, CO and many other gas-phase and surface species in the stochastic model differ from those in the deterministic models by more than an order of magnitude, at least, when tunneling is accounted for and/or diffusion energies are 3x lower than the binding energies. In this case, surface reactions, involving light species, proceed faster than accretion of the same species. In contrast, in the model without tunneling and with high binding energies, when the typical timescale of a surface recombination is greater than the timescale of accretion onto the grain, we obtain almost perfect agreement between results of Monte Carlo and deterministic calculations in the same temperature range. At lower temperatures ($\sim10$ K) gaseous and, in particular, surface abundances of most important molecules are not much affected by stochastic processes.Comment: 33 pages, 9 figures, 1 table. Accepted for publication in Ap

Enhanced production of HD and D_2 molecules on small dust grains in diffuse clouds

Motivated by recent observations of deuterated molecules in the interstellar medium, we examine the production of HD and D$_2$ molecules on dust grain surfaces. A mechanism for the enhanced production of these deuterated molecules is studied. This mechanism applies on grain surfaces on which D atoms stick more strongly than H atoms, under conditions of low flux and within a suitable range of temperatures. It is shown that under these conditions the production rates of HD and D$_2$ are greatly enhanced (vs. the H$_2$ production rate) compared with the expected rates based on the adsorption of gas-phase atomic abundances of D and H. The enhancement in the formation rate of HD is comparable with the enhancement due to gas-phase ion-molecule reactions in diffuse clouds.Comment: This is a preprint of an article accepted for publication in Monthly Notices of The Royal Astromnomical Societ

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.Comment: Accepted for publicatio

HCN J=5-4 Emission in APM08279+5255 at z=3.91

We detect HCN J=5-4 emission from the ultraluminous quasar APM08279+5255 at z=3.911 using the IRAM Plateau de Bure interferometer. This object is strongly gravitationally lensed, yet still thought to be one of the most intrinsically luminous objects in the Universe. The new data imply a line luminosity L'_HCN(J=5-4) = 4.0+/-0.5 x 10^(10) K km/s pc^2. The ~440 km/s full width half maximum of the HCN J=5-4 line matches that of the previously observed high-J CO lines in this object and suggests that the emission from both species emerges from the same region: a warm, dense circumnuclear disk. Simple radiative transfer models suggest an enhanced abundance of HCN relative to CO in the nuclear region of APM08279+5255, perhaps due to increased ionization, or possibly the selective depletion of oxygen. The ratio of far-infrared luminosity to HCN luminosity is at the high end of the range found for nearby star forming galaxies, but comparable to that observed in the few high redshift objects detected in the HCN J=1-0 line. This is the first clear detection of high-J HCN emission redshifted into the 3-millimeter atmospheric window.Comment: Accepted for publication in ApJ

The effect of grain size distribution on H2_2 formation rate in the interstellar medium

The formation of molecular hydrogen in the interstellar medium takes place on the surfaces of dust grains. Hydrogen molecules play a role in gas-phase reactions that produce other molecules, some of which serve as coolants during gravitational collapse and star formation. Thus, the evaluation of the roduction rate of hydrogen molecules and its dependence on the physical conditions in the cloud are of great importance. Interstellar dust grains exhibit a broad size distribution in which the small grains capture most of the surface area. Recent studies have shown that the production efficiency strongly depends on the grain composition and temperature as well as on its size. In this paper we present a formula which provides the total production rate of H$_2$ per unit volume in the cloud, taking into account the grain composition and temperature as well as the grain size distribution. The formula agrees very well with the master equation results. It shows that for a physically relevant range of grain temperatures, the production rate of H$_2$ is significantly enhanced due to their broad size distribution.Comment: to appear in MNRA