On the stability of nonisothermal Bonnor-Ebert spheres. III. The role of chemistry in core stabilization

Aims. We investigate the effect of chemistry on the stability of starless cores against gravitational collapse. Methods. We combine chemical and radiative transfer simulations in the context of a modified Bonnor-Ebert sphere to model the effect of chemistry on the gas temperature, and study the effect of temperature changes on core stability. Results. We find that chemistry has in general very little effect on the nondimensional radius $\xi_{\rm out}$ which parametrizes the core stability. Cores that are initially stable or unstable tend to stay near their initial states, in terms of stability (i.e., $\xi_{\rm out} \sim$ constant), as the chemistry develops. This result is independent of the initial conditions. We can however find solutions where $\xi_{\rm out}$ decreases at late times ($t \gtrsim 10^6 \, \rm yr$) which correspond to increased stabilization caused by the chemistry. Even though the core stability is unchanged by the chemistry in most of the models considered here, we cannot rule out the possibility that a core can evolve from an unstable to a stable state owing to chemical evolution. The reverse case, where an initially stable core becomes ultimately unstable, seems highly unlikely. Conclusions. Our results indicate that chemistry should be properly accounted for in studies of star-forming regions, and that further investigations of core stability especially with hydrodynamical models are warranted.Comment: 8 pages, 10 figures; accepted for publication in A&

Hydrodynamics with gas-grain chemistry and radiative transfer: comparing dynamical and static models

We quantify if the chemical abundance gradients given by a dynamical model of core collapse including time-dependent changes in density and temperature differ greatly from abundances derived from static models, where the density and temperature structures of the core are kept fixed as the chemistry evolves. For this study we developed a new one-dimensional spherically symmetric hydrodynamics code that couples the hydrodynamics equations with a comprehensive time-dependent gas-grain chemical model, including deuterium and spin-state chemistry, and radiative transfer calculations to derive self-consistent time-dependent chemical abundance gradients. We applied the code to model the collapse of a starless core up to the point when the infall flow becomes supersonic. The abundances predicted by the dynamical and static models are almost identical during the quiescent phase of core evolution, but the results start to diverge after the onset of core collapse, where the static model underestimates abundances at high medium density (inner core) and underestimates them at low density (outer core), and this is clearly reflected in simulated lines. The static model generally overestimates deuteration, which is increasingly evident the more D atoms are substituted in the molecule. We also find that using a limited chemical network, or a limited set of cooling molecules, may lead to an overestimate of the collapse timescale, and in some cases may prevent the collapse altogether. In our model, most of the line cooling near the center of the core is due to HCN, CO, and NO. In conclusion, the use of a static physical model is not a reliable method of simulating chemical abundances in starless cores after the onset of gravitational collapse. The adoption of complex chemistry and a comprehensive set of cooling molecules is necessary to model the collapse adequately.Comment: Accepted by A&A; 15 pages, 12 figures, 5 tables; arXiv abstract heavily modified and redacted from the origina

Effect of grain size distribution and size-dependent grain heating on molecular abundances in starless and pre-stellar cores

We present a new gas-grain chemical model to constrain the effect of grain size distribution on molecular abundances in starless and pre-stellar cores. We introduce grain-size dependence simultaneously for cosmic-ray (CR)-induced desorption efficiency and for grain equilibrium temperatures. We keep explicit track of ice abundances on a set of grain populations. We find that the size-dependent CR desorption efficiency affects ice abundances in a highly non-trivial way that depends on the molecule. Species that originate in the gas phase follow a simple pattern where the ice abundance is highest on the smallest grains (the most abundant in the distribution). Some molecules, such as HCN, are instead concentrated on large grains throughout the time evolution, while others (like $\rm N_2$) are initially concentrated on large grains, but at late times on small grains, due to grain-size-dependent competition between desorption and hydrogenation. Most of the water ice is on small grains at high medium density ($n({\rm H_2}) \gtrsim 10^6 \, \rm cm^{-3}$), where the water ice fraction, with respect to total water ice reservoir, can be as low as $\sim 10^{-3}$ on large (> 0.1 $\mu$m) grains. Allowing the grain equilibrium temperature to vary with grain size induces strong variations in relative ice abundances in low-density conditions where the interstellar radiation field and in particular its ultraviolet component are not attenuated. Our study implies consequences not only for the initial formation of ices preceding the starless core stage, but also for the relative ice abundances on the grain populations going into the protostellar stage. In particular, if the smallest grains can lose their mantles due to grain-grain collisions as the core is collapsing, the ice composition in the beginning of the protostellar stage could be very different to that in the pre-collapse phase.Comment: Accepted by A&A; 16 pages incl. appendices; abstract abridged to meet ArXiV requirement

HD depletion in starless cores

Aims: We aim to investigate the abundances of light deuterium-bearing species such as HD, H2D+ and D2H+ in a gas-grain chemical model including an extensive description of deuterium and spin state chemistry, in physical conditions appropriate to the very centers of starless cores. Methods: We combine a gas-grain chemical model with radiative transfer calculations to simulate density and temperature structure in starless cores. The chemical model includes deuterated forms of species with up to 4 atoms and the spin states of the light species H2, H2+ and H3+ and their deuterated forms. Results: We find that HD eventually depletes from the gas phase because deuterium is efficiently incorporated to grain-surface HDO, resulting in inefficient HD production on grains. HD depletion has consequences not only on the abundances of e.g. H2D+ and D2H+, whose production depends on the abundance of HD, but also on the spin state abundance ratios of the various light species, when compared with the complete depletion model where heavy elements do not influence the chemistry. Conclusions: While the eventual HD depletion leads to the disappearance of light deuterium-bearing species from the gas phase in a relatively short timescale at high density, we find that at late stages of core evolution the abundances of H2D+ and D2H+ increase toward the core edge and the disributions become extended. The HD depletion timescale increases if less oxygen is initially present in the gas phase, owing to chemical interaction between the gas and the dust predecing the starless core phase. Our results are greatly affected if H2 is allowed to tunnel on grain surfaces, and therefore more experimental data not only on tunneling but also on the O + H2 surface reaction in particular is needed.Comment: 14 pages, 12 figures, abstract abridged; accepted for publication in A &

A study of the cc-C3HD\mathrm{C_{3}HD}/cc-C3H2\mathrm{C_{3}H_{2}} ratio in low-mass star forming regions

We use the deuteration of $c$-$\mathrm{C_{3}H_{2}}$ to probe the physical parameters of starless and protostellar cores, related to their evolutionary states, and compare it to the $\mathrm{N_{2}H^{+}}$-deuteration in order to study possible differences between the deuteration of C- and N-bearing species. We observed the main species $c$-$\mathrm{C_{3}H_{2}}$, the singly and doubly deuterated species $c$-$\mathrm{C_{3}HD}$ and $c$-$\mathrm{C_{3}D_{2}}$, as well as the isotopologue $c$-$\mathrm{{H^{13}CC_{2}H}}$ toward 10 starless cores and 5 protostars in the Taurus and Perseus Complexes. We examined the correlation between the $N$($c$-$\mathrm{C_{3}HD}$)/$N$($c$-$\mathrm{C_{3}H_{2}}$) ratio and the dust temperature along with the $\mathrm{H_2}$ column density and the CO depletion factor. The resulting $N$($c$-$\mathrm{C_{3}HD}$)/$N$($c$-$\mathrm{C_{3}H_{2}}$) ratio is within the error bars consistent with $10\%$ in all starless cores with detected $c$-$\mathrm{C_{3}HD}$. This also accounts for the protostars except for the source HH211, where we measure a high deuteration level of $23\%$. The deuteration of $\mathrm{N_{2}H^{+}}$ follows the same trend but is considerably higher in the dynamically evolved core L1544. Toward the protostellar cores the coolest objects show the largest deuterium fraction in $c$-$\mathrm{C_{3}H_{2}}$. We show that the deuteration of $c$-$\mathrm{C_{3}H_{2}}$ can trace the early phases of star formation and is comparable to that of $\mathrm{N_{2}H^{+}}$. However, the largest $c$-$\mathrm{C_{3}H_{2}}$ deuteration level is found toward protostellar cores, suggesting that while $c$-$\mathrm{C_{3}H_{2}}$ is mainly frozen onto dust grains in the central regions of starless cores, active deuteration is taking place on ice

Nitrogen fractionation towards a pre-stellar core traces isotope-selective photodissociation

Context. Isotopologue abundance ratios are important to understand the evolution of astrophysical objects and ultimately the origins of a planetary system such as our own. With nitrogen being a fundamental ingredient of pre-biotic material, understanding its chemistry and inheritance is of fundamental importance to understand the formation of the building blocks of life. Aims. We aim to study the 14N/15N ratio in HCN, HNC, and CN across the prototypical pre-stellar core L1544. This study allows us to test the proposed fractionation mechanisms for nitrogen. Methods. We present here single-dish observations of the ground state rotational transitions of the 13C and 15N isotopologues of HCN, HNC, and CN with the IRAM 30 m telescope. We analyse their column densities and compute the 14N/15N ratio map across the core for HCN. The 15N fractionation of CN and HNC is computed towards different offsets across L1544. Results. The 15 N-fractionation map of HCN towards a pre-stellar core is presented here for the first time. Our map shows a very clear decrease in the 14N/15N ratio towards the southern edge of L1544, where carbon chain molecules present a peak, strongly suggesting that isotope-selective photodissociation has a strong effect on the fractionation of nitrogen across pre-stellar cores. The 14N/15N ratio in CN measured towards four positions across the core also shows a decrease towards the south-east of the core, while HNC shows the opposite behaviour. We also measured the 12CN/13CN ratio towards four positions across the core. Conclusions. The uneven illumination of the pre-stellar core L1544 provides clear evidence that 15 N fractionation of HCN and CN is enhanced towards the region more exposed to the interstellar radiation field. Isotope-selective photodissociation of N2 is then a crucial process to understand 15N fractionation, as already found in protoplanetary disks. Therefore, the 15N fractionation in prestellar material is expected to change depending on the environment within which pre-stellar cores are embedded. The 12CN/13CN ratio also varies across the core, but its variation does not affect our conclusions as to the effect of the environment on the fractionation of nitrogen. Nevertheless, the interplay between the carbon and nitrogen fractionation across the core warrants follow-up studies

Decomposition products of oxygen scavengers and their effect on corrosion of steam generator materials – I. Diethyl-hydroxylamine and carbohydrazide

Hydrazine used as oxygen scavenger in the secondary circuit of pressurized water reactors is hazardous to the environment and potentially carcinogenic, thus, suitable replacement chemicals for it are actively sought. In the present paper, decomposition products of two potential replacements – carbohydrazide and diethyl-hydroxylamine – are analyzed, and their effect on secondary water chemistry and corrosion of the main steam generator materials – carbon steel 22 K, stainless steel 0X18H10T and Alloy 690 – is studied by in-situ electrochemical techniques complemented by ex-situ analyses of the formed oxides by spectroscopic and microscopic methods. Quantitative interpretation of the electrochemical impedance data with the Mixed-Conduction Model allowed for the estimation of oxidation and corrosion release rates depending on scavenger formulation, alloy type and temperature. Conclusions on the extent of interaction of decomposition products with construction materials are drawn based on the experimental and calculational results.<br/

Combined model for 15N\rm ^{15}N, 13C\rm ^{13}C, and spin-state chemistry in molecular clouds

We present a new gas-grain chemical model for the combined isotopic fractionation of carbon and nitrogen in molecular clouds, in which the isotope chemistry of carbon and nitrogen is coupled with a time-dependent description of spin-state chemistry. We updated the rate coefficients of some isotopic exchange reactions considered in the literature, and present here a set of new exchange reactions involving molecules substituted in $\rm ^{13}C$ and $\rm ^{15}N$ simultaneously. We apply the model to a series of zero-dimensional simulations representing a set of physical conditions across a prototypical prestellar core, exploring the deviations of the isotopic abundance ratios in the various molecules from the elemental isotopic ratios as a function of physical conditions and time. We find that the $\rm ^{12}C/^{13}C$ ratio can deviate from the elemental ratio by up to a factor of several depending on the molecule, and that there are highly time-dependent variations in the ratios. The $\rm HCN/H^{13}CN$ ratio, for example, can obtain values of less than 10 depending on the simulation time. The $\rm ^{14}N/^{15}N$ ratios tend to remain close to the assumed elemental ratio within $\sim$ ten per cent, with no clear trends as a function of the physical conditions. Abundance ratios between $\rm ^{13}C$-containing molecules and $\rm ^{13}C$+$\rm ^{15}N$-containing molecules show somewhat increased levels of fractionation due to the newly included exchange reactions, though still remaining within a few tens of per cent of the elemental $\rm ^{14}N/^{15}N$ ratio. Our results imply the existence of gradients in isotopic abundance ratios across prestellar cores, suggesting that detailed simulations are required to interpret observations of isotopically substituted molecules correctly, especially given that the various isotopic forms of a given molecule do not necessarily trace the same gas layers.Comment: Accepted to A\&A; abstract abridged to meet arXiv requirement