A new, more comprehensive model of gas–grain chemistry in hot molecular cores is presented, in which nondiffusive reaction processes on dust-grain surfaces and in ice mantles are implemented alongside traditional diffusive surface/bulk-ice chemistry. We build on our nondiffusive treatments used for chemistry in cold sources, adopting a standard collapse/warm-up physical model for hot cores. A number of other new chemical model inputs and treatments are also explored in depth, culminating in a final model that demonstrates excellent agreement with gas-phase observational abundances for many molecules, including some (e.g., methoxymethanol) that could not be reproduced by conventional diffusive mechanisms. The observed ratios of structural isomers methyl formate, glycolaldehyde, and acetic acid are well reproduced by the models. The main temperature regimes in which various complex organic molecules (COMs) are formed are identified. Nondiffusive chemistry advances the production of many COMs to much earlier times and lower temperatures than in previous model implementations. Those species may form either as by-products of simple-ice production, or via early photochemistry within the ices while external UV photons can still penetrate. Cosmic ray-induced photochemistry is less important than in past models, although it affects some species strongly over long timescales. Another production regime occurs during the high-temperature desorption of solid water, whereby radicals trapped in the ice are released onto the grain/ice surface, where they rapidly react. Several recently proposed gas-phase COM-production mechanisms are also introduced, but they rarely dominate. New surface/ice reactions involving CH and CH2 are found to contribute substantially to the formation of certain COMs.

The detection of the amino acid glycine and its amine precursor methylamine on the comet 67P/Churyumov-Gerasimenko by the Rosetta mission provides strong evidence for a cosmic origin of prebiotics on Earth. How and when such complex organic molecules form along the process of star-and planet-formation remains debated. We report the first laboratory detection of glycine formed in the solid phase through atom and radicalradical addition surface reactions under cold dense interstellar cloud conditions. Our experiments, supported by astrochemical models, suggest that glycine forms without the need for 'energetic' irradiation, such as UV photons and cosmic rays, in interstellar water-rich ices, where it remains preserved, in a much earlier starformation stage than previously assumed. We also confirm that solid methylamine is an important sidereaction product. A prestellar formation of glycine on ice grains provides the basis for a complex and ubiquitous prebiotic chemistry in space enriching the chemical content of planet-forming material.

A prevailing theory for the interstellar production of complex organic molecules (COMs) involves formation on warm dust-grain surfaces, via the diffusion and reaction of radicals produced through grain-surface photodissociation of stable molecules. However, some gas-phase O-bearing COMs, notably acetaldehyde (CH3CHO), methyl formate (CH3OCHO), and dimethyl ether (CH3OCH3), are now observed at very low temperatures, challenging the warm scenario. Here, we introduce a selection of new nondiffusive mechanisms into an astrochemical model to account for the failure of the standard diffusive picture and to provide a more generalized scenario of COM formation on interstellar grains. New generic rate formulations are provided for cases where (i) radicals are formed by reactions occurring close to another reactant, producing an immediate follow-on reaction; (ii) radicals are formed in an excited state, allowing them to overcome activation barriers to react with nearby stable molecules; and (iii) radicals are formed through photodissociation close to a reaction partner, followed by immediate reaction. Each process occurs without thermal diffusion of large radicals. The new mechanisms significantly enhance cold COM abundances, successfully reproducing key observational results for prestellar core L1544. H abstraction from grain-surface COMs, followed by recombination, plays a crucial role in amplifying chemical desorption into the gas phase. The ultraviolet-induced chemistry produces significant COM abundances in the bulk ices, which are retained on the grains and may persist to later stages. O2 is also formed strongly in the mantle though photolysis, suggesting cometary O2 could indeed be interstellar.

Icy grain mantles are the main reservoir of the volatile elements that link chemical processes in dark, interstellar clouds with the formation of planets and composition of their atmospheres. The initial ice composition is set in the cold, dense parts of molecular clouds, prior to the onset of star formation. With the exquisite sensitivity of JWST, this critical stage of ice evolution is now accessible for detailed study. Here we show the first results of the Early Release Science program "Ice Age" that reveal the rich composition of these dense cloud ices. Weak ices, including, 13 CO 2 , OCN − , 13 CO, OCS, and COMs functional groups are now detected along two pre-stellar lines of sight. The 12 CO 2 ice profile indicates modest growth of the icy grains. Column densities of the major and minor ice species indicate that ices contribute between 2 and 19% of the bulk budgets of the key C, O, N, and S elements. Our results suggest that the formation of simple and complex molecules could begin early in a water-ice rich environment. CH 3 COCH 3 :CO (1:5) CH 3 CH 2 OH CH 3 CHO A V = 60 mag A V = 95 mag CCC s-str. CH 3 s-def. CH 3 s-def. CH 3 s-def. CH 3 a-def. CH 3 a-def.