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The origin of life on Earth involves the early appearance of an information-containing molecule such as RNA. The basic building blocks of RNA could have been delivered by carbon-rich meteorites or produced in situ by processes beginning with the synthesis of hydrogen cyanide (HCN) in the early Earth’s atmosphere. Here, we construct a robust physical and nonequilibrium chemical model of the early Earth’s atmosphere. The atmosphere is supplied with hydrogen from impact degassing of meteorites, water evaporated from the oceans, carbon dioxide from volcanoes, and methane from undersea hydrothermal vents, and in it lightning and external UV-driven chemistry produce HCN. This allows us to calculate the rain-out of HCN into warm little ponds (WLPs). We then use a comprehensive numerical model of sources and sinks to compute the resulting abundances of nucleobases, ribose, and nucleotide precursors such as 2-aminooxazole resulting from aqueous and UV-driven chemistry within them. We find that 4.4 billion years ago the limit of adenine concentrations in ponds for habitable surfaces is 0.05 ÎĽ M in the absence of seepage. Meteorite delivery of adenine to WLPs can provide boosts in concentration by 2â€"3 orders of magnitude, but these boosts deplete within months by UV photodissociation, seepage, and hydrolysis. The early evolution of the atmosphere is dominated by the decrease in hydrogen due to falling impact rates and atmospheric escape, and the rise of oxygenated species such as OH from H2O photolysis. The source of HCN is predominantly from UV radiation rather than lightning. Our work points to an early origin of RNA on Earth within ∼200 Myr of the Moon-forming impact. [ABSTRACT FROM AUTHOR]

Hydrogen cyanide (HCN) is a critical reactive source of nitrogen for building key biomolecules relevant for the origin of life. Still, many HCN reactions remain uncharacterized by experiments and theory, and the complete picture of HCN production in planetary atmospheres is not fully understood. To improve this situation, we develop a novel technique making use of computational quantum chemistry, experimental data, and atmospheric numerical simulations. First, we use quantum chemistry simulations to explore the entire field of possible reactions for a list of primary species in N2-, CH4-, and H2-dominated atmospheres. In this process, we discover 33 new reactions with no previously known rate coefficients. From here, we develop a consistent reduced atmospheric hybrid chemical network (CRAHCN) containing experimental values when available and our calculated rate coefficients otherwise. Next, we couple CRAHCN to a 1D chemical kinetic model (ChemKM) to compute the HCN abundance as a function of atmospheric depth on Titan. Our simulated atmospheric HCN profile agrees very well with the Cassini observations. CRAHCN contains 104 reactions; however, nearly all of the simulated atmospheric HCN profile can be obtained using a scaled-down network of only 19 dominant reactions. From here, we form a complete picture of HCN chemistry in Titan's atmosphere, from the dissociation of the main atmospheric species, down to the direct production of HCN along four major channels. One of these channels was first discovered and characterized in Pearce et al. and this work. [ABSTRACT FROM AUTHOR]

Observations suggest an abundance of water and a paucity of methane in the majority of observed exoplanetary atmospheres. We isolate the effect of atmospheric processes to investigate possible causes. Previously, we studied the effect of effective temperature, surface gravity, metallicity, carbon-to-oxygen ratio, and stellar type assuming cloud-free thermochemical equilibrium and disequilibrium chemistry. However, under these assumptions, methane remains a persisting spectral feature in the transmission spectra of exoplanets over a certain parameter space, the Methane Valley. In this work, we investigate the role of clouds on this domain and we find that clouds change the spectral appearance of methane in two direct ways: (1) by heating up the photosphere of colder planets and (2) by obscuring molecular features. The presence of clouds also affects methane features indirectly: (1) cloud heating results in more evaporation of condensates and hence releases additional oxygen, causing water-dominated spectra of colder carbon-poor exoplanets, and (2) HCN/CO production results in a suppression of depleted methane features by these molecules. The presence of HCN/CO and a lack of methane could be an indication of cloud formation on hot exoplanets. Cloud heating can also deplete ammonia. Therefore, a simultaneous depletion of methane and ammonia is not unique to photochemical processes. We propose that the best targets for methane detection are likely to be massive but smaller planets with a temperature around 1450 K orbiting colder stars. We also construct Spitzer synthetic color maps and find that clouds can explain some of the high-contrast observations by IRAC's channel 1 and 2. [ABSTRACT FROM AUTHOR]