O. Sipilä

The deuterium fractionation timescale in dense cloud cores: a parameter space exploration

The deuterium fraction, [N2D+]/[N2H+], may provide information about the ages of dense, cold gas structures, which are important for comparing dynamical models of cloud core formation and evolution. Here we introduce a complete chemical network with species containing up to three atoms, with the exception of the oxygen chemistry, where reactions involving H3O+ and its deuterated forms have been added, significantly improving the consistency with comprehensive chemical networks. Deuterium chemistry and spin states of H2 and H3+ isotopologues are included in this primarily gas-phase chemical model. We investigate the dependence of deuterium chemistry on these model parameters: density ({{n}H}), temperature, cosmic ray ionization rate, and gas-phase depletion factor of heavy elements ({{f}D}). We also explore the effects of time-dependent freeze-out of gas-phase species and the dynamical evolution of density at various rates relative to free-fall collapse. For a broad range of model parameters, the timescales to reach large values of Dfrac{{N2}{{H}+}}≳ 0.1, observed in some low- and high-mass starless cores, are relatively long compared to the local free-fall timescale. These conclusions are unaffected by introducing time-dependent freeze-out and considering models with evolving density, unless the initial {{f}D} ≳ 10. For fiducial model parameters, achieving Dfrac{{N2}{{H}+}}≳ 0.1 requires collapse to be proceeding at rates at least several times slower than that of free-fall collapse, perhaps indicating a dynamically important role for magnetic fields in supporting starless cores and thus the regulation of star formation.

Benchmarking spin-state chemistry in starless core models

Aims. We aim to present simulated chemical abundance profiles for a variety of important species, with special attention given to spin-state chemistry, in order to provide reference results against which present and future models can be compared. Methods. We employ gas-phase and gas-grain models to investigate chemical abundances in physical conditions corresponding to starless cores. To this end, we have developed new chemical reaction sets for both gas-phase and grain-surface chemistry, including the deuterated forms of species with up to six atoms and the spin-state chemistry of light ions and of the species involved in the ammonia and water formation networks. The physical model is kept simple in order to facilitate straightforward benchmarking of other models against the results of this paper. Results. We find that the ortho/para ratios of ammonia and water are similar in both gas-phase and gas-grain models, at late times in particular, implying that the ratios are determined by gas-phase processes. We derive late-time ortho/para ratios of ~0.5 and ~1.6 for ammonia and water, respectively. We find that including or excluding deuterium in the calculations has little effect on the abundances of non-deuterated species and on the ortho/para ratios of ammonia and water, especially in gas-phase models where deuteration is naturally hindered owing to the presence of abundant heavy elements. Although we study a rather narrow temperature range (10-20 K), we find strong temperature dependence in, e.g., deuteration and nitrogen chemistry. For example, the depletion timescale of ammonia is significantly reduced when the temperature is increased from 10 to 20 K; this is because the increase in temperature translates into increased accretion rates, while the very high binding energy of ammonia prevents it from being desorbed at 20 K.

Spin-state chemistry of deuterated ammonia

Aims. We aim to develop a chemical model that contains a consistent description of spin-state chemistry in reactions involving chemical species with multiple deuterons. We apply the model to the specific case of deuterated ammonia, to derive values for the various spin-state ratios. Methods. We apply symmetry rules in the complete scrambling assumption to calculate branching ratio tables for reactions between chemical species that include multiple protons and/or deuterons. Reaction sets for both gas-phase and grain-surface chemistry are generated using an automated routine that forms all possible spin-state variants of any given reaction with up to six H/D atoms. Single-point and modified Bonnor-Ebert models are used to study the density and temperature dependence of ammonia and its isotopologs, and the associated spin-state ratios. Results. We find that the spin-state ratios of the ammonia isotopologs are, at late times, very different from their statistical values. The ratios are rather insensitive to variations in the density, but present strong temperature dependence. We derive high peak values (

Accurate sub-millimetre rest frequencies for HOCO+ and DOCO+ ions

\sim

Understanding the C3H2 cyclic-to-linear ratio in L1544

0.1) for the deuterium fraction in ammonia, in agreement with previous (gas-phase) models. The deuterium fractionation is strongest at high density, corresponding to a high degree of depletion, and also presents temperature dependence. We find that in the temperature range 5 to 20 K, the deuterium fractionation peaks at

On the stability of nonisothermal Bonnor-Ebert spheres - II. The effect of gas temperature on the stability

\sim

Detection of Interstellar Ortho-D2H+ with SOFIA

15 K while most of the ortho/para (and meta/para for

NH3 (10-00) in the pre-stellar core L1544

\rm ND_3

Deuteration of ammonia in the starless core Ophiuchus/ H-MM1

) ratios present a minimum at 10 K (ortho/para

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

\rm NH_2D