Large prebiotic molecules in space: photo-physics of acetic acid and its isomers

An increasing number of large molecules have been positively identified in space. Many of these molecules are of biological interest and thus provide insight into prebiotic organic chemistry in the protoplanetary nebula. Among these molecules, acetic acid is of particular importance due to its structural proximity to glycine, the simplest amino acid. We compute electronic and vibrational properties of acetic acid and its isomers, methyl formate and glycolaldehyde, using density functional theory. From computed photo-absorption cross-sections, we obtain the corresponding photo-absorption rates for solar radiation at 1 AU and find them in good agreement with previous estimates. We also discuss glycolaldehyde diffuse emission in Sgr B2(N), as opposite to emissions from methyl formate and acetic acid that appear to be concentrate in the compact region Sgr B2(N-LMH).Comment: 8 pages, 5 figure

Glycolaldehyde, methyl formate and acetic acid adsorption and thermal desorption from interstellar ices

We have undertaken a detailed investigation of the adsorption, desorption and thermal processing of the astrobiologically significant isomers glycolaldehyde, acetic acid and methyl formate. Here, we present the results of laboratory infrared and temperature programmed desorption (TPD) studies of the three isomers from model interstellar ices adsorbed on a carbonaceous dust grain analogue surface. Laboratory infrared data show that the isomers can be clearly distinguished on the basis of their infrared spectra, which has implications for observations of interstellar ice spectra. Laboratory TPD data also show that the three isomers can be distinguished on the basis of their thermal desorption behaviour. In particular, TPD data show that the isomers cannot be treated the same way in astrophysical models of desorption. The desorption of glycolaldehyde and acetic acid from water-dominated ices is very similar, with desorption being mainly dictated by water ice. However, methyl formate also desorbs from the surface of the ice, as a pure desorption feature, and therefore desorbs at a lower temperature than the other two isomers. This is more clearly indicated by models of the desorption on astrophysical time-scales corresponding to the heating rate of 25 and 5 M⊙ stars. For a 25 M⊙ star, our model shows that a proportion of the methyl formate can be found in the gas phase at earlier times compared to glycolaldehyde and acetic acid. This has implications for the observation and detection of these molecules, and potentially explains why methyl formate has been observed in a wider range of astrophysical environments than the other two isomers

Trapping and desorption of complex organic molecules in water at 20 K

The formation, chemical and thermal processing of complex organic molecules (COMs) is currently a topic of much interest in interstellar chemistry. The isomers glycolaldehyde, methyl formate and acetic acid are particularly important because of their role as pre-biotic species. It is becoming increasingly clear that many COMs are formed within interstellar ices which are dominated by water. Hence the interaction of these species with water ice is crucially important in dictating their behaviour. Here we present the first detailed comparative study of the adsorption and thermal processing of glycolaldehyde, methyl formate and acetic acid adsorbed on and in water ices at astrophysically relevant temperatures (20 K). We show that the functional group of the isomer dictates the strength of interaction with water ice, and hence the resulting desorption and trapping behaviour. Furthermore, the strength of this interaction directly affects the crystallization of water, which in turn affects the desorption behaviour. Our detailed coverage and composition dependent data allow us to categorize the desorption behaviour of the three isomers on the basis of the strength of intermolecular and intramolecular interactions, as well as the natural sublimation temperature of the molecule. This categorization is extended to other C, H and O containing molecules in order to predict and describe the desorption behaviour of COMs from interstellar ices

On the formation of glycolaldehyde in dense molecular cores

Glycolaldehyde is a simple monosaccharide sugar linked to prebiotic chemistry. Recently, it was detected in a molecular core in the star-forming region G31.41+0.31 at a reasonably high abundance. We investigate the formation of glycolaldehyde at 10 K to determine whether it can form efficiently under typical dense core conditions. Using an astrochemical model, we test five different reaction mechanisms that have been proposed in the astrophysical literature, finding that a gas-phase formation route is unlikely. Of the grain-surface formation routes, only two are efficient enough at very low temperatures to produce sufficient glycolaldehyde to match the observational estimates, with the mechanism culminating in CH3OH + HCO being favored. However, when we consider the feasibility of these mechanisms from a reaction chemistry perspective, the second grain-surface route looks more promising, H3CO + HCO

Introducing v0.5 of the AI Safety Benchmark from MLCommons

This paper introduces v0.5 of the AI Safety Benchmark, which has been created by the MLCommons AI Safety Working Group. The AI Safety Benchmark has been designed to assess the safety risks of AI systems that use chat-tuned language models. We introduce a principled approach to specifying and constructing the benchmark, which for v0.5 covers only a single use case (an adult chatting to a general-purpose assistant in English), and a limited set of personas (i.e., typical users, malicious users, and vulnerable users). We created a new taxonomy of 13 hazard categories, of which 7 have tests in the v0.5 benchmark. We plan to release version 1.0 of the AI Safety Benchmark by the end of 2024. The v1.0 benchmark will provide meaningful insights into the safety of AI systems. However, the v0.5 benchmark should not be used to assess the safety of AI systems. We have sought to fully document the limitations, flaws, and challenges of v0.5. This release of v0.5 of the AI Safety Benchmark includes (1) a principled approach to specifying and constructing the benchmark, which comprises use cases, types of systems under test (SUTs), language and context, personas, tests, and test items; (2) a taxonomy of 13 hazard categories with definitions and subcategories; (3) tests for seven of the hazard categories, each comprising a unique set of test items, i.e., prompts. There are 43,090 test items in total, which we created with templates; (4) a grading system for AI systems against the benchmark; (5) an openly available platform, and downloadable tool, called ModelBench that can be used to evaluate the safety of AI systems on the benchmark; (6) an example evaluation report which benchmarks the performance of over a dozen openly available chat-tuned language models; (7) a test specification for the benchmark

Surface formation of water in interstellar ice analogs

Water is an important oxygen reservoir in space and is often used as a tracer of large-scale gas-phase dynamics in star forming regions. Moreover, it is a crucial mol. for the existence of life on Earth. To date, the exact mechanisms leading to both water formation in space and its delivery to Earth are not fully understood. In 1982, Tielens and Hagen suggested low-temp. surface chem. on icy dust grains as the main water formation route in dense mol. clouds. Furthermore, deuterated water, specifically HDO, has recently been suggested to play an important role in the understanding of the origin of water on Earth (Morbidelli et al. In the past decade, several independent labs. performed systematic studies of specific reaction routes leading to water formation under interstellar relevant conditions: H/H_2 + O/O_2/O_3 (e.g., Miyauchi et al. 2008, Matar et al. 2008, Ioppolo et al. 2008, 2010, Cuppen et al. 2010, Romanzin et al. 2011, Lamberts et al. Here, I will present an overview of the specific reaction routes within the full astrochem. reaction network leading to the surface formation of water ice. Particular attention is paid to the work performed with SURFRESIDE in Leiden. The reactants, i.e., atoms and mols., are deposited on a gold substrate at temps. ranging between 13 K and 150 K. On the cold surface, reactants can diffuse and react. Sequential deposition and co- deposition expts. are used to investigate intermediate (HO_2 and OH) and final reaction products (H_2O_2 and H_2O). The specific case of H_2 + O, a surface reaction not fully investigated in the lab., is discussed in detail. Finally, I will show the importance of studying single reaction channels for the example of HDO formation, both at low (15 K) and high (145 K) temps

Adsorption and thermal processing of glycolaldehyde, methyl formate, and acetic acid on graphite at 20 K

We present the first detailed comparative study of the adsorption and thermal processing of the three astrophysically important C2O2H4 isomers glycolaldehyde, methyl formate, and acetic acid adsorbed on a graphitic grain analogue at 20 K. The ability of the individual molecule to form intermolecular hydrogen bonds is extremely important, dictating the growth modes of the ice on the surface and the measured desorption energies. Methyl formate forms only weak intermolecular bonds and hence wets the graphite surface, forming monolayer, bilayer, and multilayer ices, with the multilayer having a desorption energy of 35 kJ mol–1. In contrast, glycolaldehyde and acetic acid dewet the surface, forming clusters even at the very lowest coverages. The strength of the intermolecular hydrogen bonding for glycolaldehyde and acetic acid is reflected in their desorption energies (46.8 and 55 kJ mol–1, respectively), which are comparable to those measured for other hydrogen-bonded species such as water. Infrared spectra show that all three isomers undergo structural changes as a result of thermal processing. In the case of acetic acid and glycolaldehyde, this can be assigned to the formation of well-ordered, crystalline, structures where the molecules form chains of hydrogen-bonded moieties. The data reported here are of relevance to astrochemical studies of hot cores and star-forming regions and can be used to model desorption from interstellar ices during the warm up phase with particular importance for complex organic molecules