Formation rates of complex organics in UV irradiated CH3OH-rich ices I: Experiments

(Abridged) Gas-phase complex organic molecules are commonly detected in the warm inner regions of protostellar envelopes. Recent models show that photochemistry in ices followed by desorption may explain the observed abundances. This study aims to experimentally quantify the broad-band UV-induced production rates of complex organics in CH3OH-rich ices at 20-70 K under ultra-high vacuum conditions. The reaction products are mainly identified by RAIRS and TPD experiments. Complex organics are readily formed in all experiments, both during irradiation and during a slow warm-up of the ices to 200 K after the UV lamp is turned off. The relative abundances of photoproducts depend on the UV fluence, the ice temperature, and whether pure CH3OH ice or CH3OH:CH4/CO ice mixtures are used. C2H6, CH3CHO, CH3CH2OH, CH3OCH3, HCOOCH3, HOCH2CHO and (CH2OH)2 are all detected in at least one experiment. The derived product-formation yields and their dependences on different experimental parameters, such as the initial ice composition, are used to estimate the CH3OH photodissociation branching ratios in ice and the relative diffusion barriers of the formed radicals. The experiments show that ice photochemistry in CH3OH ices is efficient enough to explain the observed abundances of complex organics around protostars and that ratios of complex molecules can be used to constrain their formation pathway.Comment: Accepted for publication in A&A. 65 pages including appendice

A Spectroscopic Survey of Electronic Transitions of C6_6H, 13^{13}C6_6H, and C6_6D

Electronic spectra of C$_6$H are measured in the $18\,950-21\,100$ cm$^{-1}$ domain using cavity ring-down spectroscopy of a supersonically expanding hydrocarbon plasma. In total, 19 (sub)bands of C$_6$H are presented, all probing the vibrational manifold of the B$^2\Pi$ electronically excited state. The assignments are guided by electronic spectra available from matrix isolation work, isotopic substitution experiments (yielding also spectra for $^{13}$C$_6$H and C$_6$D), predictions from ab initio calculations as well as rotational fitting and vibrational contour simulations using the available ground state parameters as obtained from microwave experiments. Besides the $0_0^0$ origin band, three non-degenerate stretching vibrations along the linear backbone of the C$_6$H molecule are assigned: the $\nu_6$ mode associated with the C-C bond vibration and the $\nu_4$ and $\nu_3$ modes associated with C$\equiv$C triple bonds. For the two lowest $\nu_{11}$ and $\nu_{10}$ bending modes, a Renner-Teller analysis is performed identifying the $\mu^2\Sigma$($\nu_{11}$) and both $\mu^2\Sigma$($\nu_{10}$) and $\kappa^2\Sigma$($\nu_{10}$) components. In addition, two higher lying bending modes are observed, which are tentatively assigned as $\mu^2\Sigma$($\nu_9$) and $\mu^2\Sigma$($\nu_8$) levels. In the excitation region below the first non-degenerate vibration ($\nu_6$), some $^2\Pi-^{2}\Pi$ transitions are observed that are assigned as even combination modes of low-lying bending vibrations. The same holds for a $^2\Pi-^{2}\Pi$ transition found above the $\nu_6$ level. From these spectroscopic data and the vibronic analysis a comprehensive energy level diagram for the B$^2\Pi$ state of C$_6$H is derived and presented.Comment: Accepted for publication in The Journal of Physical Chemistry A (26 July 2016

Porosity measurements of interstellar ice mixtures using optical laser interference and extended effective medium approximations

Aims. This article aims to provide an alternative method of measuring the porosity of multi-phase composite ices from their refractive indices and of characterising how the abundance of a premixed contaminant (e.g., CO2) affects the porosity of water-rich ice mixtures during omni-directional deposition. Methods. We combine optical laser interference and extended effective medium approximations (EMAs) to measure the porosity of three astrophysically relevant ice mixtures: H2O:CO2=10:1, 4:1, and 2:1. Infrared spectroscopy is used as a benchmarking test of this new laboratory-based method. Results. By independently monitoring the O-H dangling modes of the different water-rich ice mixtures, we confirm the porosities predicted by the extended EMAs. We also demonstrate that CO2 premixed with water in the gas phase does not significantly affect the ice morphology during omni-directional deposition, as long as the physical conditions favourable to segregation are not reached. We propose a mechanism in which CO2 molecules diffuse on the surface of the growing ice sample prior to being incorporated into the bulk and then fill the pores partly or completely, depending on the relative abundance and the growth temperature.Comment: 9 pages, 6 figures, 1 table. Accepted for publication in A&

H-atom addition and abstraction reactions in mixed CO, H2CO and CH3OH ices: an extended view on complex organic molecule formation

Complex organic molecules (COMs) have been observed not only in the hot cores surrounding low- and high- mass protostars, but also in cold dark clouds. Therefore, it is interesting to understand how such species can be formed without the presence of embedded energy sources. We present new laboratory experiments on the low-temperature solid state formation of three complex molecules: methyl formate (HC(O)OCH3), glycolaldehyde (HC(O)CH2OH) and ethylene glycol (H2C(OH)CH2OH), through recombination of free radicals formed via H-atom addition and abstraction reactions at different stages in the CO-H2CO-CH3OH hydrogenation network at 15 K. The experiments extend previous CO hydrogenation studies and aim at resembling the physical&chemical conditions typical of the CO freeze-out stage in dark molecular clouds, when H2CO and CH3OH form by recombination of accreting CO molecules and H-atoms on ice grains. We confirm that H2CO, once formed through CO hydrogenation, not only yields CH3OH through ongoing H-atom addition reactions, but is also subject to H-atom-induced abstraction reactions, yielding CO again. In a similar way, H2CO is also formed in abstraction reactions involving CH3OH. The dominant methanol H-atom abstraction product is expected to be CH2OH, while H-atom additions to H2CO should at least partially proceed through CH3O intermediate radicals. The occurrence of H-atom abstraction reactions in ice mantles leads to more reactive intermediates (HCO, CH3O and CH2OH) than previously thought, when assuming sequential H-atom addition reactions only. This enhances the probability to form COMs through radical-radical recombination without the need of UV photolysis or cosmic rays as external triggers.Comment: 20 pages, 8 figure

Relevance of the H_2 + O reaction pathway for the surface formation of interstellar water. Combined experimental and modeling study

The formation of interstellar water is commonly accepted to occur on the surfaces of icy dust grains in dark molecular clouds at low temperatures (10–20 K), involving hydrogenation reactions of oxygen allotropes. As a result of the large abundances of molecular hydrogen and atomic oxygen in these regions, the reaction H_2 + O has been proposed to contribute significantly to the formation of water as well. However, gas-phase experiments and calculations, as well as solid-phase experimental work contradict this hypothesis. Here, we use precisely executed temperature-programmed desorption (TPD) experiments in an ultra-high vacuum setup combined with kinetic Monte Carlo simulations to establish an upper limit of the water production starting from H_2 and O. These reactants were brought together in a matrix of CO_2 in a series of (control) experiments at different temperatures and with different isotopological compositions. The water detected with the quadrupole mass spectrometer upon TPD was found to originate mainly from contamination in the chamber itself. However, if water is produced in small quantities on the surface through H_2 + O, this can only be explained by a combined classical and tunneled reaction mechanism. An absolutely conservative upper limit for the reaction rate was derived with a microscopic kinetic Monte Carlo model that converts the upper limit into the highest possible reaction rate. Incorporating this rate into simulation runs for astrochemically relevant parameters shows that the upper limit to the contribution of the reaction H_2 + O in OH, and hence water formation, is 11% in dense interstellar clouds. Our combined experimental and theoretical results indicate, however, that this contribution is most likely much lower

Reaction Networks For Interstellar Chemical Modelling: Improvements and Challenges

We survey the current situation regarding chemical modelling of the synthesis of molecules in the interstellar medium. The present state of knowledge concerning the rate coefficients and their uncertainties for the major gas-phase processes -- ion-neutral reactions, neutral-neutral reactions, radiative association, and dissociative recombination -- is reviewed. Emphasis is placed on those reactions that have been identified, by sensitivity analyses, as 'crucial' in determining the predicted abundances of the species observed in the interstellar medium. These sensitivity analyses have been carried out for gas-phase models of three representative, molecule-rich, astronomical sources: the cold dense molecular clouds TMC-1 and L134N, and the expanding circumstellar envelope IRC +10216. Our review has led to the proposal of new values and uncertainties for the rate coefficients of many of the key reactions. The impact of these new data on the predicted abundances in TMC-1 and L134N is reported. Interstellar dust particles also influence the observed abundances of molecules in the interstellar medium. Their role is included in gas-grain, as distinct from gas-phase only, models. We review the methods for incorporating both accretion onto, and reactions on, the surfaces of grains in such models, as well as describing some recent experimental efforts to simulate and examine relevant processes in the laboratory. These efforts include experiments on the surface-catalysed recombination of hydrogen atoms, on chemical processing on and in the ices that are known to exist on the surface of interstellar grains, and on desorption processes, which may enable species formed on grains to return to the gas-phase.Comment: Accepted for publication in Space Science Review

Laser desorption time-of-flight mass spectrometry of ultraviolet photo-processed ices

A new ultra-high vacuum experiment is described that allows studying photo-induced chemical processes in interstellar ice analogues. MATRI2CES - a Mass Analytical Tool to study Reactions in Interstellar ICES applies a new concept by combining laser desorption and time-of-flight mass spectrometry with the ultimate goal to characterize in situ and in real time the solid state evolution of organic compounds upon UV photolysis for astronomically relevant ice mixtures and temperatures. The performance of the experimental setup is demonstrated by the kinetic analysis of the different photoproducts of pure methane (CH4) ice at 20 K. A quantitative approach provides formation yields of several new species with up to four carbon atoms. Convincing evidence is found for the formation of even larger species. Typical mass resolutions obtained range from M/M ∼320 to ∼400 for CH4 and argon, respectively. Additional tests show that the typical detection limit (in monolayers) is ≤0.02 ML, substantially more sensitive than the regular techniques used to investigate chemical processes in interstellar ices.Seventh Framework Programme (FP7)Laboratory astrophysics and astrochemistr

Desorption of CO and O2 interstellar ice analogs

Solid O2 has been proposed as a possible reservoir for oxygen in dense clouds through freeze-out processes. The aim of this work is to characterize quantitatively the physical processes that are involved in the desorption kinetics of CO-O2 ices by interpreting laboratory temperature programmed desorption (TPD) data. This information is used to simulate the behavior of CO-O2 ices under astrophysical conditions. The TPD spectra have been recorded under ultra high vacuum conditions for pure, layered and mixed morphologies for different thicknesses, temperatures and mixing ratios. An empirical kinetic model is used to interpret the results and to provide input parameters for astrophysical models. Binding energies are determined for different ice morphologies. Independent of the ice morphology, the desorption of O2 is found to follow 0th-order kinetics. Binding energies and temperature-dependent sticking probabilities for CO-CO, O2-O2 and CO-O2 are determined. O2 is slightly less volatile than CO, with binding energies of 912+-15 versus 858+-15 K for pure ices. In mixed and layered ices, CO does not co-desorb with O2 but its binding energies are slightly increased compared with pure ice whereas those for O2 are slightly decreased. Lower limits to the sticking probabilities of CO and O2 are 0.9 and 0.85, respectively, at temperatures below 20K. The balance between accretion and desorption is studied for O2 and CO in astrophysically relevant scenarios. Only minor differences are found between the two species, i.e., both desorb between 16 and 18K in typical environments around young stars. Thus, clouds with significant abundances of gaseous CO are unlikely to have large amounts of solid O2.Comment: 8 pages + 2 pages online material, 8 figures (1 online), accepted by A&

Laboratory experiments on interstellar ice analogs: The sticking and desorption of small physisorbed molecules

Molecular oxygen and nitrogen are difficult to observe since they are infrared inactive and radio quiet. The low O2 abundances found so far combined with general considerations of dense cloud conditions suggest molecular oxygen is frozen out at low temperatures (< 20 K) in the shielded inner regions of cloud cores. In solid form O2 and N2 can only be observed as adjuncts within other ice constituents, like CO. In this work we focus on fundamental properties of N2 and O2 in CO ice-gas systems, e.g. desorption characteristics and sticking probabilities at low temperatures for different ice morphologies

The formation of peptide-like molecules on interstellar dust grains

Molecules with an amide functional group resemble peptide bonds, the molecular bridges that connect amino acids, and may thus be relevant in processes that lead to the formation of life. In this study, the solid state formation of some of the smallest amides is investigated in the laboratory. To this end, CH$_{4}$:HNCO ice mixtures at 20 K are irradiated with far-UV photons, where the radiation is used as a tool to produce the radicals required for the formation of the amides. Products are identified and investigated with infrared spectroscopy and temperature programmed desorption mass spectrometry. The laboratory data show that NH$_{2}$CHO, CH$_{3}$NCO, NH$_{2}$C(O)NH$_{2}$, CH$_{3}$C(O)NH$_{2}$ and CH$_{3}$NH$_{2}$ can simultaneously be formed. The NH$_{2}$CO radical is found to be key in the formation of larger amides. In parallel, ALMA observations towards the low-mass protostar IRAS 16293-2422B are analysed in search of CH$_{3}$NHCHO (N-methylformamide) and CH$_{3}$C(O)NH$_{2}$ (acetamide). CH$_{3}$C(O)NH$_{2}$ is tentatively detected towards IRAS 16293-2422B at an abundance comparable with those found towards high-mass sources. The combined laboratory and observational data indicates that NH$_{2}$CHO and CH$_{3}$C(O)NH$_{2}$ are chemically linked and form in the ice mantles of interstellar dust grains. A solid-state reaction network for the formation of these amides is proposed.Comment: Accepted for publication in MNRA