Isotope-selective Photodissociation Research Articles

JWST Measurements of 13C, 18O, and 17O in the Atmosphere of Super-Jupiter VHS 1256 b

Abstract Isotope ratios have recently been measured in the atmospheres of directly imaged and transiting exoplanets from ground-based observations. The arrival of JWST allows us to characterize exoplanetary atmospheres in further detail and opens up wavelengths inaccessible from the ground. In this work we constrain the carbon and oxygen isotopes 13C, 18O, and 17O from CO in the atmosphere of the directly imaged companion VHS 1256 b through retrievals of the ∼4.1–5.3 μm NIRSpec G395H/F290LP observations from the early-release science program (ERS 1386). We detect and constrain 13C16O, 12C18O, and 12C17O at 32σ, 16σ, and 10σ confidence respectively, thanks to the very high signal-to-noise observations. We find the ratio of abundances are more precisely constrained than their absolute values, with 12 C / 13 C = 62 − 2 + 2 , in between previous measurements for companions (∼30) and isolated brown dwarfs (∼100). The oxygen isotope ratios are 16 O / 18 O = 425 − 28 + 33 and 16 O / 17 O = 1010 − 100 + 120 . All of the ratios are lower than the local interstellar medium and solar system, suggesting that abundances of the more minor isotopes are enhanced compared to the primary. This could be driven by isotope fractionation in protoplanetary disks, which can potentially alter the carbon and oxygen ratios through isotope selective photodissociation, gas/ice partitioning, and isotopic exchange reactions. In addition to CO, we constrain 1H 2 16 O and 12C16O2 (the primary isotopologues of both species), but find only upper limits on 12C1H4 and 14N1H3. This work highlights the power of JWST to constrain isotopes in exoplanet atmospheres, with great promise in determining formation histories in the future.

Similar levels of deuteration in the pre-stellar core L1544 and the protostellar core HH211

Context. In the centre of pre-stellar cores, deuterium fractionation is enhanced due to low temperatures and high densities. Therefore, the chemistry of deuterated molecules can be used to probe the evolution and the kinematics in the earliest stages of star formation. Aims. We analyse the deuterium fractionation of simple molecules, comparing the level of deuteration in the envelopes of the prototypical pre-stellar core L1544 in Taurus and the young protostellar core HH211 in Perseus. Methods. We used single-dish observations of CCH, HCN, HNC, and HCO+ and their 13C-, 18O-, and D-bearing isotopologues, detected with the 20 m telescope at the Onsala Space Observatory. We derived the column densities, and subsequently the carbon isotopic ratios and deuterium fractions of the molecules. Additionally, we used radiative transfer simulations and results from chemical modelling to reproduce the observed molecular lines. We used new collisional rate coefficients for HNC, HN13C DNC, and DCN that consider the hyperfine structure of these molecules. Results. For CCH, we find high levels of deuteration (10%) in both sources, consistent with other carbon chains. We find moderate deuteration of HCN (5–7%), with a slight enhancement towards the protostellar core. Equal levels of deuteration for HNC towards both cores (~8%) indicate that HNC is tracing slightly different layers compared to HCN. We find that the deuterium fraction of HCO+ is enhanced towards HH211, most likely caused by isotope-selective photodissociation of C18O. With radiative transfer, we were able to reproduce the observed lines of CCH, HCN, H13CN HNC, HN13C and DNC towards L1544 as well as CCH, H13CN HN13C DNC, H13CO+ HC18O+ and DCO+ towards HH211. Conclusions. Similar levels of deuteration show that the deuterium fractionation is most probably equally efficient towards both cores, suggesting that the protostellar envelope still retains the chemical composition of the original pre-stellar core. The fact that the two cores are embedded in different molecular clouds also suggests that environmental conditions do not have a significant effect on the deuterium fractionation within dense cores. Our results highlight the uncertainties when dealing with 13C isotopologues and the influence of the applied carbon isotopic ratio. Radiative transfer modelling shows that it is crucial to include the effects of the hyperfine structure to reproduce the observed line shapes. In addition, to correctly model emission lines from pre-stellar cores, it is necessary to include the outer layers of the core to consider the effects of extended structures. In addition to HCO+ observations, HCN observations towards L1544 also require the presence of an outer diffuse layer where the molecules are relatively abundant.

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 15N-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 15N 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 pre-stellar 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.

Modeling Nitrogen Fractionation in the Protoplanetary Disk around TW Hya: Model Constraints on Grain Population and Carbon-to-oxygen Elemental Abundance Ratio

Abstract Observations conducted using the Atacama Large Millimeter/submillimeter Array on the protoplanetary disk around TW Hya show the nitrogen fractionation of HCN molecules in HC14N/HC15N ∼ 120 at a radius of ∼20 au. In this study, we investigate the physical and chemical conditions that control this nitrogen fractionation process. To this end, a new disk model was developed, in which the isotope-selective photodissociation of N2 and isotope-exchange chemical reactions have been incorporated. Our model can successfully reproduce the observed HCN column density when the elemental abundances of gas-phase carbon and oxygen are depleted by two orders of magnitude relative to those in the interstellar medium and carbon is more abundant than oxygen ([C/O]elem > 1). The isotope-selective photodissociation of N2 is the dominant nitrogen fractionation process in our models. The observed HC14N/HC15N ratio, which increases outwards, can also be reproduced by the model by assuming that the small dust grains in the atmosphere of the outer disk are depleted more than those in the inner disk. This is consistent with grain evolution models, according to which small dust grains are continuously replenished in the inner disk due to fragmentation of the large dust grains that radially drift from the outer disk.

Carbon isotopic fractionation in molecular clouds

Context. Carbon fractionation has been studied from a theoretical point of view with different models of time-dependent chemistry, including both isotope-selective photodissociation and low-temperature isotopic exchange reactions. Aims. Recent chemical models predict that isotopic exchange reactions may lead to a depletion of 13C in nitrile-bearing species, with 12C/13C ratios two times higher than the elemental abundance ratio of 68 in the local interstellar medium. Since the carbon isotopic ratio is commonly used to evaluate the 14N/15N ratios with the double-isotope method, it is important to study carbon fractionation in detail to avoid incorrect assumptions. Methods. In this work, we implemented a gas-grain chemical model with new isotopic exchange reactions and investigated their introduction in the context of dense and cold molecular gas. In particular, we investigated the 12C/13C ratios of HNC, HCN, and CN using a grid of models, with temperatures and densities ranging from 10 to 50 K and 2 × 103 to 2 × 107 cm−3, respectively. Results. We suggest a possible 13C exchange through the 13C + C3 → 12C +13CC2 reaction, which does not result in dilution, but rather in 13C enhancement, for molecules that are formed starting from atomic carbon. This effect is efficient in a range of time between the formation of CO and its freeze-out on grains. Furthermore, the parameter-space exploration shows, on average, that the 12C/13C ratios of nitriles are predicted to be a factor 0.8–1.9 different from the local 12C/13C of 68 for high-mass star-forming regions. This result also affects the 14N/15N ratio: a value of 330 obtained with the double-isotope method is predicted to vary in the range 260–630, up to 1150, depending on the physical conditions. Finally, we studied the 12C/13C ratios of nitriles by varying the cosmic-ray ionisation rate, ζ: the 12C/13C ratios increase with ζ because of secondary photons and cosmic-ray reactions.

First detection of 13CH in the interstellar medium

In recent years, a plethora of observations with high spectral resolution of sub-millimetre and far-infrared transitions of methylidene (CH), conducted with Herschel and SOFIA, have demonstrated this radical to be a valuable proxy for molecular hydrogen that can be used for characterising molecular gas within the interstellar medium on a Galactic scale, including the CO-dark component. We report the discovery of the 13CH isotopologue in the interstellar medium using the upGREAT receiver on board SOFIA. We have detected the three hyperfine structure components of the ≈2 THz frequency transition from its X2Π1∕2 ground-state towards the high-mass star-forming regions Sgr B2(M), G34.26+0.15, W49(N), and W51E and determined 13CH column densities. The ubiquity of molecules containing carbon in the interstellar medium has turned the determination of the ratio between the abundances of the two stable isotopes of carbon, 12C/13C, into a cornerstone for Galactic chemical evolution studies. Whilst displaying a rising gradient with galactocentric distance, this ratio, when measured using observations of different molecules (CO, H2CO, and others), shows systematic variations depending on the tracer used. These observed inconsistencies may arise from optical depth effects, chemical fractionation, or isotope-selective photo-dissociation. Formed from C+ either through UV-driven or turbulence-driven chemistry, CH reflects the fractionation of C+, and does not show any significant fractionation effects, unlike other molecules that were previously used to determine the 12C/13C isotopic ratio. This makes it an ideal tracer for the 12C/13C ratio throughout the Galaxy. By comparing the derived column densities of 13CH with previously obtained SOFIA data of the corresponding transitions of the main isotopologue 12CH, we therefore derive 12C/13C isotopic ratios toward Sgr B2(M), G34.26+0.15, W49(N) and W51E. Adding our values derived from 12∕13CH to previous calculations of the Galactic isotopic gradient, we derive a revised value of 12C/13C = 5.87(0.45)RGC + 13.25(2.94).

Gas-dust chemistry of volatiles in the star and planetary system formation

AbstractThe focus of this work is on two topics: (i) formation of complex organic molecules (COMs) and (ii) isotope fractionation. Various COMs, which are C, H-containing molecules consisting of 6 atoms and more, have been detected in the central warm region of protostellar cores. Most of this review is about gas-grain chemical models, which have been constructed to evaluate the mechanisms and efficiency of the COM formation. The relevant physical and chemical processes are investigated in laboratory experiments, as reported in other articles in this volume.The isotope fractionation of volatile elements is observed in both the interstellar medium (ISM) and Solar system material. While exothermic exchange reactions enrich molecules with heavier isotopes such as Deuterium, the isotope selective photodissociation can be coupled with ice formation to enrich the ice mantle with rare isotopes. The efficiency of this fractionation depends on the photodesorption yields, which has been studied in laboratory experiments.

Probing the protoplanetary disk gas surface density distribution with 13CO emission

Context. How protoplanetary disks evolve is still an unsolved problem where different processes may be involved. Depending on the process, the disk gas surface density distribution Σgas may be very different and this could have diverse implications for planet formation. Together with the total disk mass, it is key to constrain Σgas as function of disk radius R from observational measurements. Aims. In this work we investigate whether spatially resolved observations of rarer CO isotopologues, such as 13CO, may be good tracers of the gas surface density distribution in disks. Methods. Physical-chemical disk models with different input Σgas(R) were run, taking into account CO freeze-out and isotope-selective photodissociation. The input disk surface density profiles were compared with the simulated 13CO intensity radial profiles to check whether and where the two follow each other. Results. For each combination of disk parameters, there is always an intermediate region in the disk where the slope of the 13CO radial emission profile and Σgas(R) coincide. In the inner part of the disk, the line radial profile underestimates Σgas, as 13CO emission becomes optically thick. The same happens at large radii where the column densities become too low and 13CO is not able to efficiently self-shield. Moreover, the disk becomes too cold and a considerable fraction of 13CO is frozen out, thus it does not contribute to the line emission. If the gas surface density profile is a simple power-law of the radius, the input power-law index can be retrieved within a ~20% uncertainty if one choses the proper radial range. If instead Σgas(R) follows the self-similar solution for a viscously evolving disk, retrieving the input power-law index becomes challenging, in particular for small disks. Nevertheless, we find that the power-law index γ can be in any case reliably fitted at a given line intensity contour around 6 K km s−1, and this produces a practical method to constrain the slope of Σgas(R). Application of such a method is shown in the case study of the TW Hya disk. Conclusions. Spatially resolved 13CO line radial profiles are promising to probe the disk surface density distribution, as they directly trace Σgas(R) profile at radii well resolvable by ALMA. There, chemical processes like freeze-out and isotope-selective photodissociation do not affect the emission, and, assuming that the volatile carbon does not change with radius, no chemical model is needed when interpreting the observations.

Depletion of 15N in the center of L1544: Early transition from atomic to molecular nitrogen?

We performed sensitive observations of the N15ND+(1–0) and 15NND+(1–0) lines toward the prestellar core L1544 using the IRAM 30 m telescope. The lines are not detected down to 3σ levels in 0.2 km s−1 channels of ~6 mK. The non-detection provides the lower limit of the 14N/15N ratio for N2D+ of ~700–800, which is much higher than the elemental abundance ratio in the local interstellar medium of ~200–300. The result indicates that N2 is depleted in 15N in the central part of L1544, because N2D+ preferentially traces the cold dense gas, and because it is a daughter molecule of N2. In situ chemistry is probably not responsible for the 15N depletion in N2; neither low-temperature gas phase chemistry nor isotope selective photodissociation of N2 explains the 15N depletion; the former prefers transferring 15N to N2, while the latter requires the penetration of interstellar far-ultraviolet (FUV) photons into the core center. The most likely explanation is that 15N is preferentially partitioned into ices compared to 14N via the combination of isotope selective photodissociation of N2 and grain surface chemistry in the parent cloud of L1544 or in the outer regions of L1544, which are not fully shielded from the interstellar FUV radiation. The mechanism is most efficient at the chemical transition from atomic to molecular nitrogen. In other words, our result suggests that the gas in the central part of L1544 has previously gone trough the transition from atomic to molecular nitrogen in the earlier evolutionary stage, and that N2 is currently the primary form of gas-phase nitrogen.

Nitrogen isotope fractionation in protoplanetary disks

Aims. The two stable isotopes of nitrogen, 14N and 15N, exhibit a range of abundance ratios both inside and outside the solar system. The elemental ratio in the solar neighborhood is 440. Recent ALMA observations showed HCN/HC15N ratios from 83 to 156 in six T Tauri and Herbig disks and a CN/C15N ratio of 323 ± 30 in one T Tauri star. We aim to determine the dominant mechanism responsible for these enhancements of 15N: low-temperature exchange reactions or isotope-selective photodissociation of N2. Methods. Using the thermochemical code DALI, we model the nitrogen isotope chemistry in circumstellar disks with a 2D axisymmetric geometry. Our chemical network is the first to include both fractionation mechanisms for nitrogen. The model produces abundance profiles and isotope ratios for several key N-bearing species. We study how these isotope ratios depend on various disk parameters. Results. The formation of CN and HCN is closely coupled to the vibrational excitation of H2 in the UV-irradiated surface layers of the disk. Isotope fractionation is completely dominated by isotope-selective photodissociation of N2. The column density ratio of HCN over HC15N in the disk’s inner 100 au does not depend strongly on the disk mass, the flaring angle or the stellar spectrum, but it is sensitive to the grain size distribution. For larger grains, self-shielding of N2 becomes more important relative to dust extinction, leading to stronger isotope fractionation. Between disk radii of ~50 and 200 au, the models predict HCN/HC15N and CN/C15N abundance ratios consistent with observations of disks and comets. The HCN/HC15N and CN/C15N column density ratios in the models are a factor of 2–3 higher than those inferred from the ALMA observations.

An ALMA Survey of CO Isotopologue Emission from Protoplanetary Disks in Chamaeleon I

Abstract The mass of a protoplanetary disk limits the formation and future growth of any planet. Masses of protoplanetary disks are usually calculated from measurements of the dust continuum emission by assuming an interstellar gas-to-dust ratio. To investigate the utility of CO as an alternate probe of disk mass, we use ALMA to survey 13CO and C18O J = 3–2 line emission from a sample of 93 protoplanetary disks around stars and brown dwarfs with masses from in the nearby Chamaeleon I star-forming region. We detect 13CO emission from 17 sources and C18O from only one source. Gas masses for disks are then estimated by comparing the CO line luminosities to results from published disk models that include CO freeze-out and isotope-selective photodissociation. Under the assumption of a typical interstellar medium CO-to-H2 ratio of 10−4, the resulting gas masses are implausibly low, with an average gas mass of ∼0.05 M Jup as inferred from the average flux of stacked 13CO lines. The low gas masses and gas-to-dust ratios for Cha I disks are both consistent with similar results from disks in the Lupus star-forming region. The faint CO line emission may instead be explained if disks have much higher gas masses, but freeze-out of CO or complex C-bearing molecules is underestimated in disk models. The conversion of CO flux to CO gas mass also suffers from uncertainties in disk structures, which could affect gas temperatures. CO emission lines will only be a good tracer of the disk mass when models for C and CO depletion are confirmed to be accurate.

Isotopic fractionation in interstellar molecules

AbstractThe level of isotopic fractionation in molecules provides insights into their formation environments and how they formed. In this article, we review hydrogen and nitrogen isotopic fractionation in low-mass star-forming regions. Interstellar molecules are significantly enriched in deuterium. The importance of the nuclear spin states of light species on deuterium fractionation and the usefulness of singly and doubly deuterated molecules as chemical tracers are discussed. Observations have revealed that molecules in prestellar cores are enriched in or depleted in15N depending on molecules. Compared with deuterium fractionation chemistry, our understanding of15N fractionation chemistry is not well established. We briefly discuss potential15N fractionation routes, i.e., isotopic-exchange reactions and isotopic selective photodissociation of N2. In addition, the selective freeze-out of15N atoms onto dust grains around the transition between N atoms and N2is discussed as a potential mechanism that causes the depletion of15N in the gas phase.

THE COUPLED PHYSICAL STRUCTURE OF GAS AND DUST IN THE IM Lup PROTOPLANETARY DISK

ABSTRACT The spatial distribution of gas and solids in protoplanetary disks determines the composition and formation efficiency of planetary systems. A number of disks show starkly different distributions for the gas and small grains compared to millimeter–centimeter-sized dust. We present new Atacama Large Millimeter/Submillimeter Array observations of the dust continuum, CO, 13CO, and C18O in the IM Lup protoplanetary disk, one of the first systems where this dust–gas dichotomy was clearly seen. The 12CO is detected out to a radius of 970 au, while the millimeter continuum emission is truncated at just 313 au. Based upon these data, we have built a comprehensive physical and chemical model for the disk structure, which takes into account the complex, coupled nature of the gas and dust and the interplay between the local and external environment. We constrain the distributions of gas and dust, the gas temperatures, the CO abundances, the CO optical depths, and the incident external radiation field. We find that the reduction/removal of dust from the outer disk exposes this region to higher stellar and external radiation and decreases the rate of freeze-out, allowing CO to remain in the gas out to large radial distances. We estimate a gas-phase CO abundance of 5% of the interstellar medium value and a low external radiation field (G 0 ≲ 4). The latter is consistent with that expected from the local stellar population. We additionally find tentative evidence for ring-like continuum substructure, suggestions of isotope-selective photodissociation, and a diffuse gas halo.

NITROGEN ISOTOPIC RATIO OF COMETARY AMMONIA FROM HIGH-RESOLUTION OPTICAL SPECTROSCOPIC OBSERVATIONS OF C/2014 Q2 (LOVEJOY)

ABSTRACT The icy materials present in comets provide clues to the origin and evolution of our solar system and planetary systems. High-resolution optical spectroscopic observations of comet C/2014 Q2 (Lovejoy) were performed on 2015 January 11 (at 1.321 au pre-perihelion) with the High Dispersion Spectrograph mounted on the Subaru Telescope on Maunakea, Hawaii. We derive the 14N/15N ratio of NH2 (126 ± 25), as well as the ortho-to-para abundance ratios (OPRs) of the H2O+ ion (2.77 ± 0.24) and NH2 (3.38 ± 0.07), which correspond to nuclear spin temperatures of >24 K (3σ lower limit) and 27 ± 2 K, respectively. We also derive the intensity ratio of the green-to-red doublet of forbidden oxygen lines (0.107 ± 0.007). The ammonia in the comet must have formed under low-temperature conditions at ∼10 K or less to reproduce the observed 14N/15N ratio in this molecule if it is assumed that the 15N-fractionation of ammonia occurred via ion–molecule chemical reactions. However, this temperature is inconsistent with the nuclear spin temperatures of water and ammonia estimated from the OPRs. The interpretation of the nuclear spin temperature as the temperature at molecular formation may therefore be incorrect. An isotope-selective photodissociation of molecular nitrogen by protosolar ultraviolet radiation might play an important role in the 15N-fractionation observed in cometary volatiles.

Determining protoplanetary disk gas masses from CO isotopologues line observations

Despite intensive studies of protoplanetary disks, there is still no reliable way to determine their total mass and their surface density distribution, quantities that are crucial for describing both the structure and the evolution of disks up to the formation of planets. The goal of this work is to use less abundant CO isotopologues, whose detection is routine for ALMA, to infer the gas mass of disks. Isotope-selective effects need to be taken into account in the analysis, because they can significantly modify CO isotopologues line intensities. CO isotope-selective photodissociation has been implemented in the physical-chemical code DALI and 800 disk models have been run for a range of disk and stellar parameters. Dust and gas temperature structures have been computed self-consistently, together with a chemical calculation of the main species. Both disk structure and stellar parameters have been investigated. Total fluxes have been ray-traced for different CO isotopologues and for various transitions for different inclinations. A combination of 13CO and C18O total intensities allows inference of the total disk mass, although with non-negligible uncertainties. These can be overcome by employing spatially resolved observations, i.e. the disk's radial extent and inclination. Comparison with parametric models shows differences at the factor of a few level, especially for extremely low and high disk masses. Finally, total line intensities for different CO isotopologue and for various low-J transitions are provided and are fitted to simple formulae. The effects of a lower gas-phase carbon abundance and different gas/dust ratios are investigated as well, and comparison with other tracers is made. Disk masses can be determined within a factor of a few by comparing CO isotopologue lines observations with the simulated line fluxes, modulo the uncertainties in the volatile elemental abundances.

Resolved gas cavities in transitional disks inferred from CO isotopologs with ALMA

Transitional disks around young stars are promising candidates to look for recently formed, embedded planets. Planet-disk interaction models predict that planets clear a gap in the gas while trapping dust at larger radii. Other physical mechanisms could be responsible for cavities as well. Previous observations have revealed that gas is still present inside these cavities, but the spatial distribution of this gas remains uncertain. We present high spatial resolution observations with the Atacama Large Millimeter/submillimeter Array (ALMA) of 13CO and C18O lines of four well-studied transitional disks. The observations are used to set constraints on the gas surface density, specifically cavity size and density drop inside the cavity. The physical-chemical model DALI is used to analyze the gas images of SR21, HD135344B, DoAr44 and IRS48. The main parameters of interest are the size, depth and shape of the gas cavity. CO isotope-selective photodissociation is included to properly constrain the surface density in the outer disk from C18O emission. The gas cavities are up to 3 times smaller than those of the dust in all four disks. Model fits indicate that the surface density inside the gas cavities decreases by a factor of 100-10000 compared with the surface density profile derived from the outer disk. A comparison with an analytical model of gap depths by planet-disk interaction shows that the disk viscosities are likely low, with a<1E-3 for planet masses <10 MJup. The resolved measurements of the gas and dust in transition disk cavities support the predictions of models that describe how planet-disk interactions sculpt gas disk structures and influence the evolution of dust grains. These observed structures strongly suggest the presence of giant planetary companions in transition disk cavities, although at smaller orbital radii than is typically indicated from the dust cavity radii alone.

Protoplanetary disk masses from CO isotopologue line emission

One of the methods for deriving disk masses relies on direct observations of the gas, whose bulk mass is in the outer cold ($T\lesssim30$K) regions. This zone can be well traced by rotational lines of less abundant CO isotopologues, that probe the gas down to the midplane. The total CO gas mass is then obtained with the isotopologue ratios taken to be constant at the elemental isotope values found in the local ISM. This approach is however imprecise, because isotope selective processes are ignored. The aim of this work is an isotopologue selective treatment of CO isotopologues, in order to obtain a more accurate determination of disk masses. The isotope-selective photodissociation, the main process controlling the abundances of CO isotopologues in the CO-emissive layer, is properly treated for the first time in a full disk model (DALI, Bruderer et al. 2012; Bruderer 2013). The chemistry, thermal balance, line and continuum radiative transfer are all considered together with a chemical network that treats $^{13}$CO, C$^{18}$O, C$^{17}$O, isotopes of all included atoms, and molecules, as independent species. Isotope selective processes lead to regions in the disk where the isotopologues abundance ratios are considerably different from the elemental ratio. The results of this work show that considering CO isotopologue ratios as constants can lead to an underestimate of disk masses by up to almost two orders of magnitude if grains have grown to larger sizes. This may explain observed discrepancies in mass determinations from different tracers. The dependence of the various isotopologues emission on stellar and disk parameters is investigated. Including CO isotope selective processes is crucial to determine the gas mass of the disk accurately (through ALMA observations) and thus to provide the amount of gas which may eventually form planets or change the dynamics of forming planetary systems.

The 12CO/13CO ratio in turbulent molecular clouds

The $^{13}$CO molecule is often used as a column density tracer in regions where the $^{12}$CO emission saturates. The $^{13}$CO column density is then related to that of $^{12}$CO by a uniform isotopic ratio. A similar approximation is frequently used when deriving $^{13}$CO emission maps from numerical simulations of molecular clouds. To test this assumption we calculate the $^{12}$CO/$^{13}$CO ratio self-consistently, taking the isotope selective photodissociation and the chemical fractionation of CO into account. We model the coupled chemical, thermal and dynamical evolution and the emergent $^{13}$CO emission of isolated, starless molecular clouds in various environments. Selective photodissociation has a minimal effect on the ratio, while the chemical fractionation causes a factor of 2-3 decrease at intermediate cloud depths. The variation correlates with both the $^{12}$CO and the $^{13}$CO column densities. Neglecting the depth dependence results in $\leq$60 per cent error in $^{12}$CO column densities derived from $^{13}$CO. The same assumption causes $\leq$50 per cent disparity in the $^{13}$CO emission derived from simulated clouds. We show that the discrepancies can be corrected by a fitting formula. The formula is consistent with millimetre-wavelength isotopic ratio measurements of dense molecular clouds, but underestimates the ratios from the ultraviolet absorption of diffuse regions.

Isotope selective photodissociation of N2by the interstellar radiation field and cosmic rays

Photodissociation of 14N2 and 14N15N occurs in interstellar clouds, circumstellar envelopes, protoplanetary discs, and other environments due to UV radiation from stellar sources and the presence of cosmic rays. This source of N atoms initiates the formation of complex N-bearing species and influences their isotopic composition. To study the photodissociation rates of 14N15N by UV continuum radiation and both isotopologues in a field of cosmic ray induced photons. To determine the effect of these on the isotopic composition of more complex molecules. High-resolution photodissociation cross sections of N2 are used from an accurate and comprehensive quantum- mechanical model of the molecule based on laboratory experiments. A similarly high-resolution spectrum of H2 emission following interactions with cosmic rays has been constructed. The spectroscopic data are used to calculate dissociation rates which are input into isotopically differentiated chemical models, describing an interstellar cloud and a protoplanetary disc. The dissociation rate of 14N15N in a Draine field assuming 30K excitation is 1.73x10-10s-1 and the rate due to cosmic rays assuming an H2 ionisation rate of 10-16s-1 is about 10-15s-1, with up to a factor of 10 difference between isotopologues. Shielding functions for 14N15N by 14N2, H2, and H are presented. Incorporating these into an interstellar cloud model, an enhancement of the atomic 15N/14N ratio is obtained due to the self-shielding of external radiation at an extinction of about 1.5 mag. This effect is larger where grain growth has reduced the opacity of dust to ultraviolet radiation. The transfer of photolytic isotopic fractionation N2 to other molecules is significant in a disc model, and is species dependent with 15N enhancement approaching a factor of 10 for HCN.

Carbon fractionation in photo-dissociation regions

We upgraded the chemical network from the UMIST Database for Astrochemistry 2006 to include isotopes such as ^{13}C and ^{18}O. This includes all corresponding isotopologues, their chemical reactions and the properly scaled reaction rate coefficients. We study the fractionation behavior of astrochemically relevant species over a wide range of model parameters, relevant for modelling of photo-dissociation regions (PDRs). We separately analyze the fractionation of the local abundances, fractionation of the total column densities, and fractionation visible in the emission line ratios. We find that strong C^+ fractionation is possible in cool C^+ gas. Optical thickness as well as excitation effects produce intensity ratios between 40 and 400. The fractionation of CO in PDRs is significantly different from the diffuse interstellar medium. PDR model results never show a fractionation ratio of the CO column density larger than the elemental ratio. Isotope-selective photo-dissociation is always dominated by the isotope-selective chemistry in dense PDR gas. The fractionation of C, CH, CH^+, and HCO^+ is studied in detail, showing that the fractionation of C, CH and CH^+ is dominated by the fractionation of their parental species. The light hydrides chemically derive from C^+, and, consequently, their fractionation state is coupled to that of C^+. The fractionation of C is a mixed case depending on whether formation from CO or HCO^+ dominates. Ratios of the emission lines of [C II], [C I], ^{13}CO, and H^{13}CO^+ provide individual diagnostics to the fractionation status of C^+, C, and CO.