Search

Complex Organic Molecules (COMs) have been detected in objects across different stages of stellar evolution. Many of these COMs are expected to form on interstellar ice and transfer later to the gas phase. However, due to the challenge of detecting and assigning molecules in interstellar ice observations, the only frozen COM that has been unambiguously identified is methanol. This scenario is about to change, as the exceptional capabilities of the James Webb Space Telescope (JWST) enable the observation of weak signatures of molecules in interstellar ice.This thesis has a main focus on laboratory studies to support interstellar ice observation with the JWST. The results of the spectroscopic characterization of three COMs, acetone, methylamine, and methyl cyanide mixed in interstellar ice analogs are presented in Chapters 3, 4, and 5, respectively. The potential of their absorption features to trace these species in JWST observations is also discussed. Chapter 6 presents a new experimental approach to studying morphological changes in frozen CO, which is important to understand its morphology in space. Chapter 7 presents a computational study that simulates the infrared spectra of small fullerenes (between 44-70 C atoms) and provides insights for future JWST searches for these molecules

The detection of many complex organic molecules (COMs) in interstellar space has sparked the study of their origins. While the formation of COMs detected in hot cores is attributed to photochemistry on warming grain surfaces followed by recombination of radicals and desorption, the formation routes in colder regions are still a debated issue with a number of theories such as cosmic ray bombardment on interstellar ice mantles or non-diffusive surface chemistry. Here, we present another method with reactions involving metastable atomic oxygen in the O(1D) state, which is initially produced by photodissociation of oxygen-containing species in interstellar ices. As a first example, we study the reactions of metastable oxygen atoms and methane in ices to form both formaldehyde and methanol. The reaction is studied incorporating two different surface processes: diffusive and non-diffusive chemistry. The formation of methanol and formaldehyde via metastable oxygen atoms is compared with well-known formation routes of both to understand the O(1D) contributions at different temperatures.

Many different molecular species have been observed in the interstellar medium. These range from simple diatomic species to saturated organic molecules with several carbon atoms. The latter molecules are assumed to be formed predominantely on the surface of interstellar dust grains. All surface reactions that can proceed under the low interstellar temperatures are exothermic. Their exothermicity can be as high as a few electron volts, which is considerable compared to the thermal energy of the molecules at 10 K. It is postulated that this exothermicity can be used for the desorption of reaction products from the grain. In previous studies, we have shown that translational excitation can lead to desorption, whereas vibrational and rotational excitations are much less efficient in the desorption of surface products. Vibrational excitation is however much more likely upon bond formation than translational excitation. The present study follows energy dissipation upon translational, vibrational, or rotational excitation of admolecules on a surface and its conversion, or lack thereof, to different energy contributions. To this end, thousands of molecular dynamics simulations were performed with an admolecule on top of a surface that received a fixed amount of energy, vibrational, rotational, or translational. Three different surface species have been considered, CO2, H2O, and CH4, spanning a range in binding energies, the number of internal degrees of freedom, and molecular weights. A fast exchange of energy between vibrational stretches is observed, but only very limited exchange to rotational or translation excitation has been found. For the dissipation of energy to the surface, excitation of the surface-admolecule bond is critical. Astrochemical models often assume instantaneous equipartition of energy after a reaction process to estimate the amount of available energy for chemical desorption. Based on the present study, we conclude that this assumption is not justified.

Many experimental parameters determine the chemical and physical properties of interstellar ice analogues, each of which may influence the molecular synthesis that occurs in such ices. In part 1, James et al., RSC Adv., 2020, 10, 37517, we demonstrated the effects that the stoichiometric mixing ratio had on the chemical and physical properties of CO2 : NH3 mixtures and the impact on molecular synthesis induced by thermal processing. Here, in part 2, we extend this to include 1 keV electron irradiation at 20 K of several stoichiometric mixing ratios of CO2 : NH3 ices followed by thermal processing. We demonstrate that not all stoichiometric mixing ratios of CO2 : NH3 ice form the same products. Not only did the 4 : 1 ratio form a different residue after thermal processing, but O3 was observed after electron irradiation at 20 K, which was not observed in the other ratios. For the other ratios, the residue formed from a thermal reaction similar to the work shown in Part 1. However, conversion of ammonium carbamate to carbamic acid was hindered due to electron irradiation at 20 K. Our results demonstrate the need to systematically investigate stoichiometric mixing ratios to better characterise the chemical and physical properties of interstellar ice analogues to further our understanding of the routes of molecular synthesis under different astrochemical conditions.

Temperature programmed desorption has been used to probe the distribution of binding energies of carbon monoxide (CO) to molecular solid thin films of astrophysical relevance. Measurements are reported for solid water (both compact amorphous solid water and crystalline water), ammonia, and methanol surfaces. Binding energy distributions and optimized pre-exponential factors based on the inversion method are tabulated. These are compared to existing data on these systems and astrophysical conclusions drawn.

In this study, we employed broadband X-rays ($6-2000$ eV) to irradiate the frozen acetone CH$_3$COCH$_3$, at the temperature of 12 K, with different photon fluences up to $2.7\times 10^{18}$ photons cm$^{-2}$. Here, we consider acetone as a representative complex organic molecule (COM) present on interstellar ice grains. The experiments were conduced at the Brazilian synchrotron facility (LNLS/CNPEN) employing infrared spectroscopy (FTIR) to monitor chemical changes induced by radiation in the ice sample. We determined the effective destruction cross-section of the acetone molecule and the effective formation cross-section for daughter species. Chemical equilibrium, obtained for fluence $2\times 10^{18}$ photons cm$^{-2}$, and molecular abundances at this stage were determined, which also includes the estimates for the abundance of unknown molecules, produced but not detected, in the ice. Timescales for ices, at hypothetical snow line distances, to reach chemical equilibrium around several compact and main-sequence X-ray sources are given. We estimate timescales of 18 days, 3.6 and 1.8 months, $1.4\times 10^9-6\times 10^{11}$ years, 600 and $1.2\times 10^7$ years, and $10^7$ years, for the Sun at 5 AU, for O/B stars at 5 AU, for white dwarfs at 1 LY, for the Crab pulsar at 2.25 LY, for Vela pulsar at 2.25 LY, and for Sagittarius A* at 3 LY, respectively. This study improves our current understanding about radiation effects on the chemistry of frozen material, in particular, focusing for the first time, the effects of X-rays produced by compact objects in their eventual surrounding ices., Comment: Accepted in MNRAS. This is a preprint. 14 pages, 7 figures

分子雲に存在する星間氷を模した紫外線照射非晶質氷（水・メタノール・アンモニアの混合氷）が 60-150 K の温度範囲で，従来考えられてきた固体状態ではなく，液体的にふるまうことが発見された． また，純粋な水からなる氷も低温での紫外線照射により，50-140 K で液体状になり，紫外線照射で現 れる液体的なふるまいが水氷に特徴的な現象であることが明らかとなった．液体は化学反応を促進す るため，星間氷の液体的なふるまいは，生命材料有機物にも関連する複雑有機物の形成を助長する可 能性がある．また，液体状の氷は塵の効率的な付着を助ける可能性もあり，惑星形成の第一歩である 塵の集積過程の理解にもつながると期待される．, The recent discovery of the liquid-like behavior of water-dominated interstellar ice analog suggests that the ice analog may enhance the formation of organic compounds, including prebiotic molecules, as well as the accretion of icy dust, to form icy planetesimals under certain interstellar conditions.

No statistical study of COMs toward a large sample of high-mass protostars with ALMA has been carried out so far. We aim to study six N-bearing species: CH$_3$CN, HNCO, NH$_2$CHO, C$_2$H$_5$CN, C$_2$H$_3$CN and CH$_3$NH$_2$ in a large sample of high-mass protostars. From the ALMAGAL survey, 37 of the most line-rich hot molecular cores are selected. Next, we fit their spectra and find column densities and excitation temperatures of the above N-bearing species, in addition to CH$_3$OH. We (tentatively) detect CH$_3$NH$_2$ in $\sim32%$ of the sources. We find three groups of species when comparing their excitation temperatures: hot (NH$_2$CHO; Tex > 250 K), warm (C$_2$H$_3$CN, HN$^{13}$CO and CH$_{3}^{13}$CN; 100 K < Tex < 250 K) and cold species (CH$_3$OH and CH$_3$NH$_2$; Tex < 100 K). This temperature segregation reflects the trend seen in their sublimation temperatures and validates the idea of onion-like structure of COMs around protostars. Moreover, the molecules studied here show constant column density ratios across low- and high-mass protostars with scatter less than a factor $\sim3$ around the mean. The constant column density ratios point to a common formation environment of COMs or their precursors, most likely in the pre-stellar ices. The scatter around the mean of the ratios, although small, varies depending on the species considered. This spread can either have a physical origin (source structure, line or dust optical depth) or a chemical one. Formamide is most prone to the physical effects as it is tracing the closest regions to the protostars, whereas such effects are small for other species. Assuming that all molecules form in the pre-stellar ices, the scatter variations could be explained by differences in lifetimes or physical conditions of the pre-stellar clouds. If the pre-stellar lifetimes are the main factor, they should be similar for low- and high-mass protostars., 49 pages, 46 figures, Accepted for publication in A&A

Context. A variety of laboratory ice spectra simulating different chemical environments, ice morphology as well as thermal and energetic processing are demanded to provide an accurate interpretation of the infrared spectra of protostars. To answer which combination of laboratory data best fit the observations, an automated statistically-based computational approach becomes necessary. Aims. To introduce a new approach, based on evolutionary algorithms, to search for molecules in ice mantles via spectral decomposition of infrared observational data with laboratory ice spectra. Methods. A publicly available and open-source fitting tool, called ENIIGMA (dEcompositioN of Infrared Ice features using Genetic Modelling Algorithms), is introduced. The tool has dedicated Python functions to carry out continuum determination of the protostellar spectra, silicate extraction, spectral decomposition and statistical analysis to calculate confidence intervals and quantify degeneracy. As an assessment of the code, several tests were conducted with known ice samples and constructed mixtures. A complete analysis of the Elias 29 spectrum was performed as well. Results. The ENIIGMA fitting tool can identify the correct ice samples and their fractions in all checks with known samples tested in this paper. Concerning the Elias 29 spectrum, the broad spectral range between 2.5-20 $\mu$m was successfully decomposed after continuum determination and silicate extraction. This analysis allowed the identification of different molecules in the ice mantle, including a tentative detection of CH$_3$CH$_2$OH. Conclusions. The ENIIGMA is a toolbox for spectroscopy analysis of infrared spectra that is well-timed with the launch of the James Webb Space Telescope. Additionally, it allows for exploring the different chemical environments and irradiation fields in order to correctly interpret astronomical observations., Comment: 23 pages, 19 figures, 3 tables. Accepted for publication in A&A

High-resolution gas phase spectroscopy techniques in the microwave, millimeter-wave and terahertz spectral ranges can be used to study complex organic molecules desorbed from interstellar ice analogues surface with a high sensitivity. High-resolution gas phase spectroscopy gives unambiguous information about the molecular composition, the molecular structure, and transition frequencies needed for their detection by radio telescopes in various interstellar and circumstellar environments. The results will be useful not only for interpreting astronomical spectra and understanding astrophysical processes, but also for more general studies of gas-surface chemistry. This paper presents a new experimental approach based on a combination of a chirped-pulse Fourier transform microwave spectrometer detection and a low temperature surface desorption experiment. The experimental set-up is benchmarked on the desorption of ammonia ice detected by high-resolution gas phase microwave spectroscopy., Comment: accepted on Earth Space and Chemistry

Biomolecules can be synthesized in interstellar ice grains subject to UV radiation and cosmic rays. I show that on time scales of $\gtrsim 10^{6}$ years, these processes lead to the formation of large percolation clusters of organic molecules. Some of these clusters would have ended up on proto-planets where large, loosely bound aggregates of clusters (superclusters) would have formed. The interior regions of such superclusters provided for chemical micro-environments that are filtered versions of the outside environment. I argue that models for abiogenesis are more likely to work when considered inside such micro-environments. As the supercluster breaks up, biochemical systems in such micro-environments gradually become subject to a less filtered environment, allowing them to get adapted to the more complex outside environment. A particular system originating from a particular location on some supercluster would have been the first to get adapted to the raw outside environment and survive there, thereby becoming the first microbe. A collision of a microbe-containing proto-planet with the Moon could have led to fragments veering off back into space, microbes in small fragments would have been able to survive a subsequent impact with the Earth., Comment: 13 pages. Progress in Biophysics and Molecular Biology (2019)

The surfaces of interstellar and circumstellar dust grains are the sites of molecule formation, most of which, except H2, stick and form ice mantles. The study of ice evolution thus seems directly relevant for understanding our own origins, although the relation between interstellar and solar system ices remains a key question. The comparison of interstellar and solar system ices relies evidently on an accurate understanding of the composition and processes in both environments. With the accurate in situ measurements available for the comet 67P/Churyumov-Gerasimenko with the Rosetta mission, improving our understanding of interstellar ices is the more important. Here, I will address three specific questions. First, while laboratory experiments have made much progress in understanding complex organic molecule (COM) formation in the ices, the question remains, how does COM formation depend on environment and time? Second, what is the carrier of sulfur in the ices? And third, can ice absorption bands trace the processing history of the ices? Laboratory experiments, ranging from infrared spectroscopy to identify interstellar ice species, to surface experiments to determine reaction parameters in ice formation scenarios, to heating and irradiation experiments to simulate space environments, are essential to address these questions and analyze the flood of new observational data that will become available with new facilities in the next 2-10 years.

Chemistry in the interstellar medium is generally out-of-equilibrium and as such is kinetically controlled by a set of time-dependent equations, both for gas-phase chemistry and solid-state chemistry. The competition between the different possible reactions will determine toward which complex molecules the chemical network is driven to. The formation of complex molecules on the surface of the grains or in the ice mantle covering them is set by the diffusion-reaction equation, which is depending on temperature dependent reaction rate constants and diffusion coefficients. This paper shows how these two parameters can be experimentally determined by laboratory experiments. It also shows how the ice mantle reorganization plays an important role in the trapping and reactivity, which leads to the formation of complex organic molecules.

We elucidate mechanisms of electron-induced radiolysis in cosmic (interstellar, planetary, and cometary) ice analogs of ammonia (NH3), likely the most abundant nitrogen-containing compound in the i...

The abundance of interstellar ice constituents is usually expressed with respect to the water ice because, in denser regions, a significant portion of the interstellar grain surface would be covered by water ice. The binding energy (BE), or adsorption energy of the interstellar species regulates the chemical complexity of the interstellar grain mantle. Due to the high abundance of water ice, the BE of surface species with the water is usually provided and widely used in astrochemical modeling. However, the hydrogen molecules would cover some part of the grain mantle in the denser and colder part of the interstellar medium. Even at around ~ 10K, few atoms and simple molecules with lower adsorption energies can migrate through the surface. The BE of the surface species with H2 substrate would be very different from that of a water substrate. However, adequate information regarding these differences is lacking. Here, we employ the quantum chemical calculation to provide the BE of 95 interstellar species with H2 substrate. These are representative of the BEs of species to a H2 overlayer on a grain surface. On average, we notice that the BE with the H2 monomer substrate is almost ten times lower than the BE of these species reported earlier with the H2 O c-tetramer configuration. The encounter desorption of H and H2 was introduced (with ED (H, H2 ) =45 K and ED (H2 , H2 ) =23 K) to have a realistic estimation of the abundances of the surface species in the colder and denser region. Our quantum chemical calculations yield higher adsorption energy of H2 than that of H (ED (H, H2 ) = 23 - 25 K and ED (H2, H2 ) =67 - 79 K). We further implement an astrochemical model to study the effect of encounter desorption with the resent realistic estimation. The encounter desorption of the N atom (calculations yield ED (N, H2 ) =83 K) is introduced to study the differences with its inclusion., 16 pages, 8 Figures

The adsorption of a series of atoms and small molecules and radicals (H, C, N, O, NH, OH, H2O, CH3, and NH3) on hexagonal crystalline and amorphous ice clusters were obtained via classical molecular dynamics and electronic structure methods. The geometry and binding energies were calculated using a QMHigh:QMLow hybrid method on model clusters. Several combination of basis sets, density functionals and semi-empirical methods were compared and tested against previous works. More accurate binding energies were also refined via single point Coupled Cluster calculations. Most species, except carbon atom, physisorb on the surface, leading to rather small binding energies. The carbon atom forms a COH2 molecule and in some cases leads to the formation of a COH-H3O+ complex. Amorphous ices are characterized by slightly stronger binding energies than the crystalline phase. A major result of this work is to also access the dispersion of the binding energies since a variety of adsorption sites is explored. The interaction energies thus obtained may serve to feed or refine astrochemical models. The present methodology could be easily extended to other types of surfaces and larger adsorbates.

Hexamethylentetramine has drawn a lot of attention due to its potential to produce prebiotic species. This work aims to gain a better understanding in the chemical processes concerning methylamine under astrophysically relevant conditions. In particular, this work deeps into the formation of N-heterocycles in interstellar ice analogues exposed to UV radiation, which may lead to the formation of prebiotic species. Experimental simulations of interstellar ice analogues were carried out in ISAC. ISAC is an ultrahigh vacuum chamber equipped with a cryostat, where gas and vapour species are frozen forming ice samples. Infrared and ultraviolet spectroscopy were used to monitor the solid phase, and quadrupole mass spectrometry served to measure the composition of the gas phase. The variety of species detected after UV irradiation of ices containing methylamine revealed the presence of 12 species which have been already detected in the ISM, being 4 of them typically classified as complex organic molecules: formamide (HCONH 2 ), methyl cyanide (CH3 CN), CH3 NH and CH3 CHNH. Warming up of the irradiated CH3 NH2 -bearing ice samples lead to the formation of trimethylentriamine (TMT), a N-heterocycle precursor of HMT, and the subsequent synthesis of HMT at temperatures above 230 K., We would like to devote this paper to the memory of our long- term colleague and dearest friend professor Rafael Escribano from Spanish CSIC, whose advise and stimulating discussions we en- joyed so much. The Spanish Ministry of Science, Innovation and Universities supported this research under grant number AYA2017- 85322-R and MDM-2017-0737 Unidad de Excelencia ‘Mar ́ıa de Maeztu’– Centro de Astrobiología (CSIC-INTA). (AEI/FEDER, UE). PCG acknowledges support from PGC2018-096444-B-I00. HC was supported by PhD fellowship FPU-17/03172. MLS ac- knowledges Ministerio de Economía y Competitividad of Spain for the project AGL2016-80475-R and Comunidad Autónoma of Madrid (Spain) and European funding from FEDER program (project S2018/BAA-4393, AVANSECAL-II-CM).

We propose a new model for treating solid-phase photoprocesses in interstellar ice analogues. In this approach, photoionization and photoexcitation are included in more detail, and the production of electronically-excited (suprathermal) species is explicitly considered. In addition, we have included non-thermal, non-diffusive chemistry to account for the low-temperature characteristic of cold cores. As an initial test of our method, we have simulated two previous experimental studies involving the UV irradiation of pure solid O$_2$. In contrast to previous solid-state astrochemical model calculations which have used gas-phase photoabsorption cross-sections, we have employed solid-state cross-sections in our calculations. This method allows the model to be tested using well-constrained experiments rather than poorly constrained gas-phase abundances in ISM regions. Our results indicate that inclusion of non-thermal reactions and suprathermal species allows for reproduction of low-temperature solid-phase photoprocessing that simulate interstellar ices within cold ($\sim$ 10 K) dense cores such as TMC-1., Comment: ApJ, accepted: 15 pages, 3 figures

Context. The molecular composition of interstellar ice mantles is defined by gas-grain processes in molecular clouds, with the main components being $H_2O$, $CO$, and $CO_2$. $CH_3OH$ ice is detected towards the denser regions, where large amounts of $CO$ freeze out and get hydrogenated. Heating from nearby protostars can further change the ice structure and composition. Despite the several observations of icy features towards molecular clouds and along the line of site of protostars, it is not yet clear if interstellar ices are mixed or if they have a layered structure. Aims. We aim to examine the effect of mixed and layered ice growth in ice mantle analogues, with focus on the position and shape of methanol infrared bands, so future observations could shed light on the structure of interstellar ices in different environments. Methods. Mixed and layered ice samples were deposited on a cold substrate kept at T = 10 K using a closed-cycle cryostat placed in a vacuum chamber. The spectroscopic features were analysed by FTIR spectroscopy. Different proportions of the most abundant four molecules in ice mantles, namely $H_2O$, $CO$, $CO_2$, and $CH_3OH$, were investigated, with special attention on the analysis of the $CH_3OH$ bands. Results. We measure changes in the position and shape of the CH and CO stretching bands of $CH_3OH$ depending on the mixed or layered nature of the ice sample. Spectroscopic features of methanol are also found to change due to heating. Conclusions. A layered ice structure best reproduces the $CH_3OH$ band position recently observed towards a pre-stellar core and in star-forming regions. Based on our experimental results, we conclude that observations of $CH_3OH$ ices can provide information about the structure of interstellar ices, and we expect JWST to put stringent constraints on the layered or mixed nature of ices in different interstellar environments., Comment: 11 pages, 8 figures, 3 tables

Context. Many C-, O-, and H-containing complex organic molecules (COMs) have been observed in the interstellar medium (ISM) and their formation has been investigated in laboratory experiments. An increasing number of recent detections of large N-bearing COMs motivates our experimental investigation of their chemical origin. Aims. We investigate the potential role of acetonitrile (CH3CN) as a parent molecule to N-bearing COMs, motivated by its omnipresence in the ISM and structural similarity to another well-known precursor species, CH3OH. The aim of the present work is to characterize the chemical complexity that can result from vacuum UV photolysis of a pure CH3CN ice and a more realistic mixture of H2O:CH3CN. Methods. The CH3CN ice and H2O:CH3CN ice mixtures were UV irradiated at 20 K. Laser desorption post ionization time-of-flight mass spectrometry was used to detect the newly formed COMs in situ. We examined the role of water in the chemistry of interstellar ices through an analysis of two different ratios of H2O:CH3CN (1:1 and 20:1). Results. We find that CH3CN is an excellent precursor to the formation of larger nitrogen-containing COMs, including CH3CH2CN, NCCN/CNCN, and NCCH2CH2CN. During the UV photolysis of H2O:CH3CN ice, the water derivatives play a key role in the formation of molecules with functional groups of: imines, amines, amides, large nitriles, carboxylic acids, and alcohols. We discuss possible formation pathways for molecules recently detected in the ISM. © ESO 2021. Acknowledgements. M.B. and H.L. acknowledge the European Union (EU) and Horizon 2020 funding awarded under the Marie Skłodowska-Curie action to the EUROPAH consortium (grant number 722346) as well as NOVA 5 funding. Additional funding has been realized through a NWO-VICI grant. This work has been supported by the Danish National Research Foundation through the Center of Excellence “InterCat” (Grant agreement no.: DNRF150). We thank N. F. W. Ligterink, A. G. G. M. Tielens, J. Terwischa van Scheltinga, J. Bouwman and T. Lamberts for helpful discussions.

Relevant information on the origins of the solar system and the early evolution of life itself can be derive from systematic and controlled exploration of water ice here on Earth. Therefore, over the last decades, a huge effort on experimental methodologies has been made to study the multiple crystal ice phases, which are observed outside our home–gravitational–potential. By employing (100)–oriented MgO lattice surface as a microcantilever sensor, we conducted the first ever study on the dynamics of the Structural Phase Transition at 185 K in water ice by means of coherent elastic scattering of electron diffraction. We estimate the amount of phonons caused by this transition applying precise quantum computing key tools, and resulting in a maximum value of 1.23 ± 0.02. Further applications of our microcantilever sensor were assessed using unambiguous mapping of the surface stress induced by the c($$4 \times 2$$ 4 × 2 ) → p($$3 \times 2$$ 3 × 2 ) Structural Phase Transition of the interstellar ice formulated on the Williamsom–Hall model. This development paves the way and thus establishes an efficient characterization tool of the surface mechanical strains of materials with potential applications arising from interstellar ice inclusive glaciers to the wide spectrum of solid–state physics.

Complex organic molecules (COMs) have been identified toward high- and low-mass protostars as well as molecular clouds. Among them, sugar-like and polyol two carbon-bearing molecules such as glycolaldehyde (GA) and ethylene glycol (EG) are of special interest. Recent laboratory experiments have shown that they can efficiently be formed via atom addition reactions between accreting H-atoms and CO molecules or via energetic processes (UV, electrons) on ice analogues containing methanol or formaldehyde. In this study, we report new laboratory experiments on the low-temperature solid state formation of complex organic molecules – the first sugar glyceraldehyde and its saturated derivative glycerol – through VUV photolysis performed at three different temperatures (15, 50, and 90 K) of astrochemically relevant ices composed of water and formaldehyde. We get evidence that the species production depends on the ice temperature during photolysis. The results presented here indicate that a general scheme of aldose and polyol formation is plausible and that heavier COMs than GA and EG could exist in interstellar environments. We propose a general pathway involving radical-formaldehyde reactions as common initiation step for aldose and polyol formation. Future telescope observations may give additional clues on their presence in star-forming regions as observations are currently limited because of the detection thresholds.

Spectroscopic studies play a key role in the identification and analysis of interstellar ices and their structure. Some molecules have been identified within the interstellar ices either as pure, mixed, or even as layered structures. Absorption band features of water ice can significantly change with the presence of different types of impurities (CO, CO2, CH3OH, H2CO, etc.). In this work, we carried out a theoretical investigation to understand the behavior of water band frequency, and strength in the presence of impurities. The computational study has been supported and complemented by some infrared spectroscopy experiments aimed at verifying the effect of HCOOH, NH3 , and CH3 OH on the band profiles of pure H2O ice. Specifically, we explored the effect on the band strength of libration, bending, bulk stretching, and free-OH stretching modes. Computed band strength profiles have been compared with our new and existing experimental results, thus pointing out that vibrational modes of H2O and their intensities can change considerably in the presence of impurities at different concentrations. In most cases, the bulk stretching mode is the most affected vibration, while the bending is the least affected mode. HCOOH was found to have a strong influence on the libration, bending, and bulk stretching band profiles. In the case of NH3, the free-OH stretching band disappears when the impurity concentration becomes 50%. This work will ultimately aid a correct interpretation of future detailed spaceborne observations of interstellar ices by means of the upcoming JWST mission., Comment: Accepted for Publication in the ACS Earth and Space Chemistry Journal

Pure methane (CH4) ices processed by energetic electrons under ultra-high vacuum conditions to simulate secondary electrons formed via galactic cosmic rays (GCRs) penetrating interstellar ice mantles have been shown to produce an array of complex hydrocarbons with the general formulae: CnH2n+2 (n = 4-8), CnH2n (n = 3-9), CnH2n-2 (n = 3-9), CnH2n-4 (n = 4-9), and CnH2n-6 (n = 6-7). By monitoring the in situ chemical evolution of the ice combined with temperature programmed desorption (TPD) studies and tunable single photon ionization coupled to a reflectron time-of-flight mass spectrometer, specific isomers of C3H4, C3H6, C4H4, and C4H6 were probed. These experiments confirmed the synthesis of methylacetylene (CH3CCH), propene (CH3CHCH2), cyclopropane (c-C3H6), vinylacetylene (CH2CHCCH), 1-butyne (HCCC2H5), 2-butyne (CH3CCCH3), 1,2-butadiene (H2CCCH(CH3)), and 1,3-butadiene (CH2CHCHCH2) with yields of 2.17 ± 0.95 × 10-4, 3.7 ± 1.5 × 10-3, 1.23 ± 0.77 × 10-4, 1.28 ± 0.65 × 10-4, 4.01 ± 1.98 × 10-5, 1.97 ± 0.98 × 10-4, 1.90 ± 0.84 × 10-5, and 1.41 ± 0.72 × 10-4 molecules eV-1, respectively. Mechanistic studies exploring the formation routes of methylacetylene, propene, and vinylacetylene were also conducted, and revealed the additional formation of the 1,2,3-butatriene isomer. Several of the above isomers, methylacetylene, propene, vinylacetylene, and 1,3-butadiene, have repeatedly been shown to be important precursors in the formation of polycyclic aromatic hydrocarbons (PAHs), but until now their interstellar synthesis has remained elusive.

Methylamine (CH3NH2) and methanimine (CH2NH) represent essential building blocks in the formation of amino acids in interstellar and cometary ices. In our study, by exploiting isomer selective detection of the reaction products via photoionization coupled with reflectron time of flight mass spectrometry (Re-TOF-MS), we elucidate the formation of methanimine and ethylenediamine (NH2CH2CH2NH2) in methylamine ices exposed to energetic electrons as a proxy for secondary electrons generated by energetic cosmic rays penetrating interstellar and cometary ices. Interestingly, the two products methanimine and ethylenediamine are isoelectronic to formaldehyde (H2CO) and ethylene glycol (HOCH2CH2OH), respectively. Their formation has been confirmed in interstellar ice analogs consisting of methanol (CH3OH) which is ioselectronic to methylamine. Both oxygen-bearing species formed in methanol have been detected in the interstellar medium (ISM), while for methanimine and ethylenediamine only methanimine has been identified so far. In comparison with the methanol ice products and our experimental findings, we predict that ethylenediamine should be detectable in these astronomical sources, where methylamine and methanimine are present.

This paper reports the first extensive study of the existence and effects of interstellar hydrogen bonding. The reactions that occur on the surface of the interstellar dust grains are the dominant processes by which interstellar molecules are formed. Water molecules constitute about 70% of the interstellar ice. These water molecules serve as the platform for hydrogen bonding. High level quantum chemical simulations for the hydrogen bond interaction between 20 interstellar molecules (known and possible) and water are carried out using different ab-intio methods. It is evident that if the formation of these species is mainly governed by the ice phase reactions, there is a direct correlation between the binding energies of these complexes and the gas phase abundances of these interstellar molecules. Interstellar hydrogen bonding may cause lower gas abundance of the complex organic molecules (COMs) at the low temperature. From these results, ketenes whose less stable isomers that are more strongly bonded to the surface of the interstellar dust grains have been observed are proposed as suitable candidates for astronomical observations.

There are two different adsorption states of CO on amorphous solid water (ASW): one adsorption state consists of CO interacting with non-hydrogen-bonded (dangling) OH, while the other consists of CO interacting with bonded OH. Photoirradiation onto ASW at 157 nm induces CO2 formation through the reaction of CO with OH, where OH originates from the photodissociation of H2O ice. The preferential formation of CO2 would explain the missing infrared CO band in the observation of interstellar ice particles.

Complex organic molecules (COMs) may have played a role in the formation of life in the early Earth (Herbst & van Dishoeck (2009)). Here we present the formation of NH2CHO and CH3CHO upon vacuum-ultraviolet (VUV) irradiation of CO:NH3 and CO:CH4 ice mixtures, simulating the UV processing of interstellar ices in the interior of dense clouds. We have found that the conversion from ${\rm{N}}{{\rm{H}}_{\dot 2}}$ radicals to NH2CHO is 4–15 times higer than that from ${\rm{N}}{{\rm{H}}_{\dot 3}}$ to CH3CHO, probably due to the competing formation of larger hydrocarbons in the latter case.

In the recent studies it is observed that not only ion/radical-molecule gas-phase reactions, but also solid-state reactions on icy dust grains play an important role for the formation of new species. Molecular hydrogen (H2) is the most abundant molecule in the interstellar medium (ISM) in gas phase and it has been assumed to exist in solid state or as coating on grains. The work is mainly focused on the hydrogenation of CN radical in interstellar ice analogs for astronomically relevant temperatures. The solid H2 can act as a hydrogenation agent, reacting with CN radicals to form HCN. Hydrogenation reactions of CN radical have been studied by Hartree-Fock (HF) and Density Functional Theory (DFT) methods. We have discussed that, how molecules form when CN containing ices are exposed to thermal hydrogen atoms. The present work deals with possibility of the formation of HCN by hydrogenation via radical molecule reactions in gas phase as well as in PCM and the effect of temperature on thermodynamical parameter.

Aims. Understanding the desorption properties and sublimation temperatures of CO is key toward constraining the astrophysical regimes within which CO exists in the gas and ice phases. Previous experimental studies using temperature programmed desorption (TPD) determined the binding energies of 12CO and 13CO without the precision that is necessary to determine the effect of isotopes on these properties, which is required when analyzing astronomical data of CO isotopologues. The purpose of this work is to precisely determine the binding energies of 12CO and 13CO. Methods. We conducted experiments using temperature interval desorption (TID), which ensures that thermal equilibrium is reached at each temperature, as well as TPD experiments on interstellar analogues of 12CO and 13CO ices. Results. Sublimation curves show a small but distinct separation between 12CO and 13CO ices. We found that complete sublimation of pure 12CO occurs at 28.9 ± 0.2 K and pure 13CO at 29.0 ± 0.2 K. A systematic difference of 0.1 K was found for 13CO ice compared to 12CO ice under similar desorption conditions, implying that the binding energy in the ice phase for 13CO ice is higher than that of 12CO. Our experimentally derived binding energies were determined through TID to be (12CO–12CO)Eb = (833 ± 5 K) and (13CO–13CO)Eb = (848 ± 6 K). Our results quantitatively show that 13CO is more tightly bound than 12CO in the ice phase, which could have a significant effect on CO isotopic enrichment in astrophysical settings.

para-Hydrogen (p-H2) serves as a new host in matrix-isolation experiments for an investigation of species of astrochemical interest. Protonated and mono-hydrogenated species are produced upon electron bombardment during deposition of p-H2 containing a precursor in a small proportion. The applications of this novel technique to generate protonated polycyclic aromatic hydrocarbons (H+PAH), protonated polycyclic nitrogen heterocycles (H+PANH), and their neutral counterparts, which are important in the identification of interstellar unidentified infrared emission bands, demonstrate its superiority over other methods. The clean production with little fragmentation, ease of distinction between protonated and neutral species, narrow lines and reliable relative infrared intensities of the lines, and broad coverage of the spectral range associated with this method enable us to assign the isomers unambiguously. The application of this method to the protonation of small molecules is more complicated partly because of the feasible fragmentation and reactions, and partly because of the possible proton sharing between the species of interest and H2, but, with isotopic experiments and secondary photolysis, definitive assignments are practicable. Furthermore, the true relative infrared intensities are critical to a comparison of experimental results with data from theoretical calculations. The spectra of a proton-shared species in solid p-H2 might provide insight into a search for spectra of proton-bound species in interstellar media. Investigations of hydrogenated species involving the photolysis of Cl2 or precursors of OH complement those using electron bombardment and provide an improved ratio of signal to noise. With careful grouping of observed lines after secondary photolysis and a comparison with theoretical predictions, various isomers of these species have been determined. This photolytic technique has been applied in an investigation of hydrogenated PAH and PANH, and the hydrogenation reactions of small molecules, which are important in interstellar ice and the evolution of life. The electronic transitions of molecules in solid p-H2 have been little investigated. The matrix shift of the origins of transitions and the spectral width seem to be much smaller than those of noble-gas matrices; these features might facilitate a direct comparison of matrix spectra with diffuse interstellar bands, but further data are required to assess this possibility. The advantages and disadvantages of applying these techniques of p-H2 matrix isolation to astrochemical research and their future perspectives are discussed.

Dust grains in cold, dense interstellar clouds build up appreciable ice mantles through the accretion and subsequent surface chemistry of atoms and molecules from the gas. These mantles, of thicknesses on the order of 100 monolayers, are primarily composed of H2O, CO, and CO2. Laboratory experiments using interstellar ice analogues have shown that porosity could be present and can facilitate diffusion of molecules along the inner pore surfaces. However, the movement of molecules within and upon the ice is poorly described by current chemical kinetics models, making it difficult either to reproduce the formation of experimental porous ice structures or to extrapolate generalized laboratory results to interstellar conditions. Here we use the off-lattice Monte Carlo kinetics model MIMICK to investigate the effects that various deposition parameters have on laboratory ice structures. The model treats molecules as isotropic spheres of a uniform size, using a Lennard-Jones potential. We reproduce experimental trends in the density of amorphous solid water (ASW) for varied deposition angle, rate and surface temperature; ice density decreases when the incident angle or deposition rate is increased, while increasing temperature results in a more-compact water ice. The models indicate that the density behaviour at higher temperatures (≥80 K) is dependent on molecular rearrangement resulting from thermal diffusion. To reproduce trends at lower temperatures, it is necessary to take account of non-thermal diffusion by newly-adsorbed molecules, which bring kinetic energy both from the gas phase and from their acceleration into a surface binding site. Extrapolation of the model to conditions appropriate to protoplanetary disks, in which direct accretion of water from the gas-phase may be the dominant ice formation mechanism, indicate that these ices may be less porous than laboratory ices.

Phosphine (PH3) is an important molecule in the chemistry of phosphorus (P)-bearing species in the interstellar medium. Interstellar PH3 is thought to primarily form on icy grains, where several surface processes may occur during and after its formation. To better understand the physicochemical behavior of PH3 on icy grains in dense molecular clouds, we performed experimental and computational studies on the reactions of phosphine with H and D atoms at low temperatures. We found that phosphine and its deuterated isotopologue PD3 are released into the gas phase from icy surfaces (porous amorphous, compact amorphous, and crystalline ice) via chemical desorption. Even though the effective desorption cross section did not vary between the different icy surfaces, the desorption fraction was smallest for porous amorphous ice. We confirmed that, at 10 K on icy surfaces, H-D substitution reactions of PH3 and D-H substitution reactions of PD3 occurred following reactions with D and H atoms, respectively. Because the activation barrier for the abstraction of H or D atoms from phosphine is similar to 1500 K, quantum tunneling should play a role at low temperatures. Under the present experimental conditions, the H-D substitution reaction of PH3 was slightly slower than the D-H substitution reaction of PD3. Therefore, the rates of the H-D and D-H substitution reactions should not be constrained by tunneling reactions but rather by other elementary processes such as atom diffusion on ice. Our experimental results suggest the possible presence of a deuterated phosphine isotopologue (PH2D) in PH3-rich interstellar environments.