Deuterated water: partition functions and equilibrium constants

HDO and D₂O are thought to be present in significant quantities in the coldest regions of the Universe. Partition functions are calculated for these species and used to calculate temperature dependent equilibrium constants for the most important fractionation reactions involving water. HDO may also be a key indicator of the absence of deuterium burning in very low mass stars. The HDO partition function calculation is extended to high  ( T ≤ 6000 K)  temperatures for this purpose.     

Deuterium enrichment of the interstellar medium

Despite the low elemental abundance of atomic deuterium in the interstellar medium (ISM), observational evidence suggests that several species, both in the gas phase and in ices, could be heavily fractionated. We explore various aspects of deuterium enrichment by constructing a chemical evolution model in both gaseous and granular phases. Depending on various physical parameters, gases and grains are allowed to interact with each other through the exchange of their chemical species. It is known that HCO⁺ and N₂H⁺ are two abundant gas phase ions in the ISM and, their deuterium fractionation is generally used to predict the degree of ionization in the various regions of a molecular cloud. For a more accurate estimation, we consider the density profile of a collapsing cloud. The radial distributions of important interstellar molecules, along with their deuterated isotopomers, are presented. Quantum chemical simulations are computed to study the effects of isotopic substitution on the spectral properties of these interstellar species. We calculate the vibrational (harmonic) frequencies of the most important deuterated species (neutral and ions). The rotational and distortional constants of these molecules are also computed in order to predict the rotational transitions of these species. We compare vibrational (harmonic) and rotational transitions as computed by us with existing experimental and theoretical results. It is hope that our results will assist observers in detecting several hitherto unobserved deuterated species.     

Charge transfer reactions at interfaces between neutral gas and plasma: Dynamical effects and X‐ray emission

Charge‐transfer is the main process linking neutrals and charged particles in the interaction regions of neutral (or partly ionized) gas with a plasma. In this paper we illustrate the importance of charge‐transfer with respect to the dynamics and the structure of neutral gas‐plasma interfaces. We consider the following phenomena: (1) the heliospheric interface ‐ region where the solar wind plasma interacts with the partly‐ionized local interstellar medium (LISM) and (2) neutral interstellar clouds embedded in a hot, tenuous plasma such as the million degree gas that fills the so‐called “Local Bubble”. In (1), we discuss several effects in the outer heliosphere caused by charge exchange of interstellar neutral atoms and plasma protons. In (2) we describe the role of charge exchange in the formation of a transition region between the cloud and the surrounding plasma based on a two‐component model of the cloud‐plasma interaction. In the model the cloud consists of relatively cold and dense atomic hydrogen gas, surrounded by hot, low density, fully ionized plasma. We discuss the structure of the cloud‐plasma interface and the effect of charge exchange on the lifetime of interstellar clouds. Charge transfer between neutral atoms and minor ions in the plasma produces X‐ray emission. Assuming standard abundances of minor ions in the hot gas surrounding the cold interstellar cloud, we estimate the X‐ray emissivity consecutive to the charge transfer reactions. Our model shows that the charge‐transfer X‐ray emission from the neutral cloud‐plasma interface may be comparable to the diffuse thermal X‐ray emission from the million degree gas cavity itself (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Calculations on the rates, mechanisms, and interstellar importance of the reactions between C and NH2 and between N and CH2

The attempt to understand the temperature dependence of the HNC/HCN abundance ratio in interstellar clouds has been long standing and indecisive. In this paper we report quantum chemical and dynamical studies of two neutral–neutral reactions thought to be important in the formation of HNC and HCN, respectively – C+NH₂→HNC+H, and N+CH₂→HCN+H. We find that although these reactions do lead initially to the products suggested by astronomers, there is so much excess energy available in both reactions that the HCN and HNC products are able to undergo efficient isomerization reactions after production. The isomerization leads to near equal production rates of the two isomers, with HNC slightly favoured if there is sufficient rotational excitation. This result has been incorporated into our latest chemical model network of dense interstellar clouds.     

Circular polarimetry and the line of sight to the Becklin–Neugebauer object

The 3.1-μm absorption feature of water-ice has been observed spectroscopically in many molecular clouds and, when it has been observed spectropolarimetrically, usually a corresponding polarization feature is seen. Typically, on these occasions, and particularly for the Becklin–Neugebauer (BN) object, a distinct position angle shift between the feature and continuum is seen, which indicates both a fractionation of the icy material and a changing alignment direction along the line of sight.
Here, the dependence of circular polarimetry on fractionation along the line of sight is investigated and it is shown that the form of its spectrum, together with the sign of the position angle shift, indicates where along the line of sight the icy material lies. More specifically, a coincidence between the sign of the position angle displacement in the ice feature, measured north through east, and that of the circular polarization ice feature means that the icy grains are overlaid by bare grains. Some preliminary circular polarimetry of BN has this characteristic, and a similar situation is found in the only two other cases for which relevant observations so far exist.     

Charge exchange in massive star‐forming regions

As a result of feedback from massive stars, via their intense winds and/or supernova explosions, massive star‐forming regions are entirely filled with hot, X‐ray emitting plasmas, which escape into the ambient ISM. As shown recently by Townsley et al. for several “extreme” cases (Carina, M17, NGC 3576, NGC 3603, 30 Dor), by way of large Chandra ACIS mosaics, extra, non‐thermal emission lines are present on top of the standard lines emitted by hot plasmas. Some of them are very close to lines characteristic of charge‐exchange reactions between the hot plasma and the cold surrounding material, suggesting that this mechanism operates on large spatial scales (several 10 pc) in star‐forming regions in general. The connection with starburst galaxies is briefly mentioned, and it is pointed out that supernovae interacting with molecular clouds may also provide a good environment to look for charge exchange processes (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Molecular signatures of MHD waves

The small ion-neutral drift speeds attained in MHD waves lead to a significant increase in the rates of several important ion-molecule reactions. The effect on the deuterium chemistry of dark clouds could allow MHD wave motion to be observed directly. The results of some recent observations to test this theory are outlined.     

HE 1127–1304: the largest radio quasar

By considering the propagation of low-amplitude magnetohydrodynamic waves in partially ionized plasmas, it is shown that the ion-neutral drift (ambipolar diffusion) induced by the waves can have specific effects on the molecular chemistry of cold material. The chemistry occurring in gas swept by Alfvén waves is described and it is shown that this leads to spatial variations in the deuterium fractionation ratios of, for example, HCO⁺ and N₂H⁺, on spatial scales of a few hundredths of a parsec, depending upon the fractional ionization of the ambient medium. The possibility of detecting interstellar Alfvén waves by molecular spectroscopy and their effect of producing small-scale chemical abundance gradients in molecular clouds are briefly discussed.     

Calculations of ion-molecule deuterium fractionation reactions involving HD

Gas-phase chemical models of deuterium fractionation in dense interstellar clouds utilize a small number of exothermic reactions to achieve fractionation. Although HD is a major repository of deuterium, it appears not to exchange deuterium with many molecular ions. Useful semiquantitative reasons have been given for the unusual lack of reactivity of exothermic ion-HD deuterium exchange systems, but quantum chemical studies are needed to understand these ideas in more detail and to determine if the lack of reactivity pertains at very low temperatures not studied in the laboratory, or whether tunneling can drive the reactions. Accordingly, the potential energy surfaces of three representative ion-molecule exchange reactions involving protonated ions (H3+, CH3+, HCO+) and HD have been investigated with ab initio quantum chemical techniques. Our results generally confirm the semiquantitative picture as to which reactions are likely to occur and show that tunneling at low temperatures is unlikely to alter this picture.     

A new, efficient stellar evolution code for calculating complete evolutionary tracks

We present a new stellar evolution code and a set of results, demonstrating its capability at calculating full evolutionary tracks for a wide range of masses and metallicities. The code is fast and efficient, and is capable of following through all evolutionary phases, without interruption or human intervention. It is meant to be used also in the context of modelling the evolution of dense stellar systems, for performing live calculations for both normal star models and merger products.
The code is based on a fully implicit, adaptive-grid numerical scheme that solves simultaneously for structure, mesh and chemical composition. Full details are given for the treatment of convection, equation of state, opacity, nuclear reactions and mass loss.
Results of evolutionary calculations are shown for a solar model that matches the characteristics of the present sun to an accuracy of better than 1 per cent; a  1 M_⊙  model for a wide range of metallicities; a series of models of stellar Populations I and II, for the mass range 0.25 to  64 M_⊙  , followed from pre-main-sequence to a cool white dwarf or core collapse. An initial–final mass relationship is derived and compared with previous studies. Finally, we briefly address the evolution of non-canonical configurations, merger products of low-mass main-sequence parents.     

Chemical effects of H2 formation excitation

The effects of the production on dust grain surfaces of molecular hydrogen in excited states have been investigated. On the assumption that all of the H₂ formed on the surface of grains has a sufficient level of excitation too vercome the energy barriers in the formation reactions for the important OH and CH⁺ radicals, we consider the likely abundances of excited H₂ (H₂ ^*), OH and CH⁺ in various situations. Two different models are employed; the first links the H₂ ^* abundance directly to that of H₂ using a steady-state approximation, whilst the second considers the time-dependence of H₂ ^*. The second model is applied to gas that has been subjected to a strong isothermal shock (specifically, the shock-induced collapse of a diffuse cloud), which results in an extreme (high density, high atomic hydrogen abundance) environment. In general, it is found that the presence of the excited H₂ has only marginal effects on the chemistry of interstellar clouds. However, in the isothermal shock model, the abundances of CH⁺ are significantly enhanced, but only on short timescales, whilst the effects on the OH abundances are smaller, but last longer. We conclude that other than in such exceptional environments there are no obvious chemical signatures of the formation of H₂ ^*. This revised version was published online in July 2006 with corrections to the Cover Date.     

SO and SiO emission around the young cluster in the CB 34 globule

The globule CB 34, which harbours a cluster of class 0 young stellar object (YSO) protostars, has been investigated through a multiline SO and SiO survey at millimetre wavelengths. The SO data reveal that the globule consists of three quiescent high-density (∼10⁵ cm⁻³) clumps, labelled A, B and C, with sizes of ∼  0.2–0.3 pc  . The SiO data provide evidence for high-velocity gas across the globule. Most likely, the high-velocity gas is distributed in three distinct high-velocity outflows associated with the YSOs in each of the three clumps. High-velocity SO features have been detected only towards the two brightest SiO outflows. These broad SO components exhibit spatial and spectral distributions which are consistent with those of the SiO emission, so they can also be used as tracers of the outflows.
The comparison between the spatial and spectral properties of the SO and SiO emissions in the three clumps suggests different evolutionary stages for the embedded YSOs. In particular, the YSO associated with clump C exhibits some peculiarities, namely smaller SiO linewidths, lower SiO column densities, a lack of extended SiO structure and of SO wings, and the presence of a SO spatial distribution which is displaced with respect to the location of the YSO. This behaviour is well explained if the SiO and SO molecules which were produced at high velocities in the shocked region have been destroyed or slowed down because of the interaction with the ambient medium, and the chemistry is dominated again by low-temperature reactions. Thus our observations strongly suggest that the YSO in clump C is in a more evolved phase than the other members of the cluster.     

Ultra-high-resolution observations of CH in Southern Molecular Cloud envelopes

We present a mini-survey of ultrahigh-resolution spectroscopy (UHRS) of CH towards three southern molecular cloud envelopes. The sightlines are selected to probe physically similar gas in different Galactic environments. With a velocity resolution of ∼0.5 km s⁻¹  ( R =575 000)  these observations resolve most kinematic components of the absorption lines. We do, however, detect one line component in the Lupus region, which is not resolved and for which an upper limit of   b <0.3 km s^-1  is found. We find a correlation between distance of the absorbing gas from the Galactic mid-plane and the fractional abundance of CH. We show that this correlation can be explained as being a result of a fall-off in the ultraviolet radiation field intensity and propose that CH observations in carefully selected sightlines might allow a mapping of the variations in the interstellar radiation field.     

New models of interstellar gas–grain chemistry – II. Surface photochemistry in quiescent cores

The photodissociation of surface species, caused by photons from the cosmic-ray-induced and background interstellar radiation fields, is incorporated into our combined gas-phase and grain-surface chemical models of quiescent dense interstellar cores. For the cores studied here, only cosmic-ray-induced photons are important. We find that photodissociation alters gas-phase and surface abundances mainly at large cloud ages (≳ 10^6–7 yr). The abundances of those surface species, such as H₂O, that are readily reproduced on the surface following photodissociation are not strongly affected at any time. The abundances of surface species that are, on the other hand, reformed slowly via surface reactions possessing activation energy (e.g. CH₃OH) are reduced, while the abundances of associated surface photoproducts (e.g. CO) increase. In the gas phase, inclusion of surface photodissociation tends to increase molecular abundances at late times, slightly improving the agreement with observation for TMC-1.     

The formation of molecular clouds

In a recent paper, Elmegreen has made a cogent case, from an observational point of view, that the lifetimes of molecular clouds are comparable to their dynamical time-scales. If so, this has important implications for the mechanisms by which molecular clouds form. In particular, we consider the hypothesis that molecular clouds may form not by in situ cooling of atomic gas, but rather by the agglomeration of the dense phase of the interstellar medium, much, if not most, of which is already in molecular form.     

Unlocking the Keyhole: H2 and PAH emission from molecular clumps in the Keyhole Nebula

To better understand the environment surrounding CO emission clumps in the Keyhole Nebula, we have made images of the region in H₂ 1–0 S(1) (2.122-μm) emission and polycyclic aromatic hydrocarbon (PAH) emission at 3.29 μm. Our results show that the H₂ and PAH emission regions are morphologically similar, existing as several clumps, all of which correspond to CO emission clumps and dark optical features. The emission confirms the existence of photodissociation regions (PDRs) on the surface of the clumps. By comparing the velocity range of the CO emission with the optical appearance of the H₂ and PAH emission, we present a model of the Keyhole Nebula whereby the most negative velocity clumps are in front of the ionization region, the clumps at intermediate velocities are in it and those which have the least negative velocities are at the far side. It may be that these clumps, which appear to have been swept up from molecular gas by the stellar winds from η  Car, are now being overrun by the ionization region and forming PDRs on their surfaces. These clumps comprise the last remnants of the ambient molecular cloud around η Car.     

Molecular cloud abundances and anomalous diffusion

The chemistry of molecular clouds has been studied for decades, with an increasingly general and sophisticated treatment of the reactions involved. Yet the treatment of turbulent diffusion has remained extremely sketchy, assuming simple Fickian diffusion with a scalar diffusivity D. However, turbulent flows similar to those in the interstellar medium are known to give rise to anomalous diffusion phenomena, more specifically superdiffusion (increase of the diffusivity with the spatial scales involved). This paper considers to what extent and in what sense superdiffusion modifies molecular abundances in interstellar clouds. For this first exploration of the subject we employ a very rough treatment of the chemistry and the effect of non‐uniform cloud density on the diffusion equation is also treated in a simplified way. The results nevertheless clearly demonstrate that the effect of superdiffusion is quite significant, abundance values at a given radius being modified by order of unity factors. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The effect of grain size distribution on H2 formation rate in the interstellar medium

The formation of molecular hydrogen  (H₂)  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 production 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 that provides the total production rate of  H₂  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  H₂  is significantly enhanced due to their broad size distribution.     

When is star formation episodic? A delay differential equation 'negative feedback' model

We introduce a differential equation for star formation in galaxies that incorporates negative feedback with a delay. When the feedback is instantaneous, solutions approach a self-limiting equilibrium state. When there is a delay, even though the feedback is negative, the solutions can exhibit cyclic and episodic solutions. We find that periodic or episodic star formation only occurs when two conditions are satisfied. First the delay time-scale must exceed a cloud consumption time-scale. Secondly, the feedback must be strong. This statement is quantitatively equivalent to requiring that the time-scale to approach equilibrium be greater than approximately twice the cloud consumption time-scale. The period of oscillations predicted is approximately four times the delay time-scale. The amplitude of the oscillations increases with both feedback strength and delay time.
We discuss applications of the delay differential equation (DDE) model to star formation in galaxies using the cloud density as a variable. The DDE model is most applicable to systems that recycle gas and only slowly remove gas from the system. We propose likely delay mechanisms based on the requirement that the delay time is related to the observationally estimated time between episodic events. The proposed delay time-scale accounting for episodic star formation in galaxy centres on periods similar to   P ∼ 10 Myr  , irregular galaxies with   P ∼ 100 Myr  , and the Milky Way disc with   P ∼ 2  Gyr, could be that for exciting turbulence following creation of massive stars, that for gas pushed into the halo to return and interact with the disc and that for spiral density wave evolution, respectively.     

Molecular line intensities as measures of cloud masses – I. Sensitivity of CO emissions to physical parameter variations

A reliable estimate of the molecular gas content in galaxies plays a crucial role in determining their dynamical and star-forming properties. However, H₂, the dominant molecular species, is difficult to observe directly, particularly in the regions where most molecular gas is thought to reside. Its mass is therefore commonly inferred by assuming a direct proportionality with the integrated intensity of the  ¹²CO( J = 1 → 0)  emission line, using a CO-to-H₂ conversion factor, X . Although a canonical value for X is used extensively in such estimates, there is increasing evidence, both theoretical and observational, that the conversion factor may vary by over an order of magnitude under conditions different from those of the local neighbourhood. In an effort to understand the influence of changing environmental conditions on the conversion factor, we derive theoretical estimates of X for a wide range of physical parameters using a photon-dominated region (PDR) time-dependent chemical model, benchmarking key results against those of an independent PDR code to ensure reliability. Based on these results, the sensitivity of the X factor to change in each physical parameter is interpreted in terms of the chemistry and physical processes within the cloud. In addition to confirming previous observationally derived trends, we find that the time-dependence of the chemistry, often neglected in such models, has a considerable influence on the value of the conversion factor.