Hydrogen cyanide (HCN) is a key feedstock molecule for the production of life's building blocks. The formation of HCN in an N$_2$-rich atmospheres requires first that the triple bond between N$\equiv$N be severed, and then that the atomic nitrogen find a carbon atom. These two tasks can be accomplished via photochemistry, lightning, impacts, or volcanism. The key requirements for producing appreciable amounts of HCN are the free availability of N$_2$ and a local carbon to oxygen ratio of C/O $\geq 1$. We discuss the chemical mechanisms by which HCN can be formed and destroyed on rocky exoplanets with Earth-like N$_2$ content and surface water inventories, varying the oxidation state of the dominant carbon-containing atmospheric species. HCN is most readily produced in an atmosphere rich in methane (CH$_4$) or acetylene (C$_2$H$_2$), but can also be produced in significant amounts ($> 1$ ppm) within CO-dominated atmospheres. Methane is not necessary for the production of HCN. We show how destruction of HCN in a CO$_2$-rich atmosphere depends critically on the poorly-constrained energetic barrier for the reaction of HCN with atomic oxygen. We discuss the implications of our results for detecting photochemically produced HCN, for concentrating HCN on the planet's surface, and its importance for prebiotic chemistry.
There are two dominant and contrasting classes of origin of life scenarios: those predicting that life emerged in submarine hydrothermal systems, where chemical disequilibrium can provide an energy source for nascent life; and those predicting that life emerged within subaerial environments, where UV catalysis of reactions may occur to form the building blocks of life. Here, we describe a prebiotically plausible environment that draws on the strengths of both scenarios: surface hydrothermal vents. We show how key feedstock molecules for prebiotic chemistry can be produced in abundance in shall…
The effect of protoplanetary differentiation on the fate of life essential volatiles like nitrogen and carbon and its subsequent effect on the dynamics of planetary growth is unknown. Because the dissolution of nitrogen in magma oceans depends on its partial pressure and oxygen fugacity, it is an ideal proxy to track volatile redistribution in protoplanets as a function of their sizes and growth zones. Using high pressure and high temperature experiments in graphite undersaturated conditions, here we show that the iron loving character of nitrogen is an order of magnitude higher than previous …
Molecular nitrogen is the most commonly assumed background gas that supports habitability on rocky planets. Despite its chemical inertness, nitrogen molecule is broken by lightning, hot volcanic vents, and bolide impacts, and can be converted into soluble nitrogen compounds and then sequestered in the ocean. The very stability of nitrogen, and that of nitrogen-based habitability, is thus called into question. Here we determine the lifetime of molecular nitrogen vis-a-vis aqueous sequestration, by developing a novel model that couples atmospheric photochemistry and oceanic chemistry. We find th…
Volatile molecules containing hydrogen, carbon, and nitrogen are key components of planetary atmospheres. In the pebble accretion model for rocky planet formation, these volatile species are accreted during the main planetary formation phase. For this study, we modelled the partitioning of volatiles within a growing planet and the outgassing to the surface. The core stores more than 90\% of the hydrogen and carbon budgets of Earth for realistic values of the partition coefficients of H and C between metal and silicate melts. The magma oceans of Earth and Venus are sufficiently deep to undergo …
Understanding the origin of life-essential volatiles like N in the Solar System and beyond is critical to evaluate the potential habitability of rocky planets. Whether the inner Solar System planets accreted these volatiles from their inception or had an exogenous delivery from the outer Solar System is, however, not well understood. Using previously published data of nucleosynthetic anomalies of Ni, Mo, W and Ru in iron meteorites along with their 15N-14N ratios, here we show that the earliest formed protoplanets in the inner and outer protoplanetary disk accreted isotopically distinct N. Whi…
We predict that cyanoacetylene (HC$_3$N) is produced photochemically in the atmosphere of GJ 1132 b in abundances detectable by the James Webb Space Telescope (JWST), assuming that the atmosphere is hydrogen dominated and rich in molecular nitrogen (N$_2$), methane (CH$_4$) and hydrogen cyanide (HCN), as described by Swain et al. (2021). First, we construct line list and cross-sections for HC$_3$N. Then we apply these cross-sections and the model atmosphere of Swain et al. (2021) to a radiative transfer model in order to simulate the transmission spectrum of GJ 1132 b as it would be seen by JW…
The atmospheres of gaseous giant exoplanets orbiting close to their parent stars (hot Jupiters) have been probed for nearly two decades. They allow us to investigate the chemical and physical properties of planetary atmospheres under extreme irradiation conditions. Previous observations of hot Jupiters as they transit in front of their host stars have revealed the frequent presence of water vapour and carbon monoxide in their atmospheres; this has been studied in terms of scaled solar composition under the usual assumption of chemical equilibrium. Both molecules as well as hydrogen cyanide wer…
One of the key goals of exoplanet science is the atmospheric characterisation of super-Earths. Atmospheric abundances provide insight on the formation and evolution of those planets and help to put our own rocky planets in context. Observations on 55 Cancri e point towards a N-dominated atmosphere. In this paper we explore this possibility, showing which will be the most abundant gases and observable species in emission and transmission spectroscopy of such an atmosphere. We use analytical arguments and observed parameters to estimate the possible thermal profile of the atmosphere and test thr…
Ocean-vaporizing impacts of chemically reduced planetesimals onto the early Earth have been suggested to catalyse atmospheric production of reduced nitrogen compounds and trigger prebiotic synthesis despite an oxidized lithosphere. While geochemical evidence supports a dry, highly reduced late veneer on Earth, the composition of late-impacting debris around lower-mass stars is subject to variable volatile loss as a result of their hosts' extended pre-main sequence phase. We perform simulations of late-stage planet formation across the M-dwarf mass spectrum to derive upper limits on reducing bo…
Low-mass stars show evidence of vigorous magnetic activity in the form of large flares and coronal mass ejections. Such space weather events may have important ramifications for the habitability and observational fingerprints of exoplanetary atmospheres. Here, using a suite of three-dimensional coupled chemistry-climate model (CCM) simulations, we explore effects of time-dependent stellar activity on rocky planet atmospheres orbiting G-, K-, and M-dwarf stars. We employ observed data from the MUSCLES campaign and Transiting Exoplanet Satellite Survey and test a range of rotation period, magnet…
Planets smaller than Neptune and larger than Earth make up the majority of the discovered exoplanets. Those with H$_2$-rich atmospheres are prime targets for atmospheric characterization. The transition between the two main classes, super-Earths and sub-Neptunes, is not clearly understood as the rocky surface is likely not accessible to observations. Tracking several trace gases (specifically the loss of ammonia (NH$_3$) and hydrogen cyanide (HCN)) has been proposed as a proxy for the presence of a shallow surface. In this work, we revisit the proposed mechanism of nitrogen conversion in detai…
We modeled the transit signatures in the Lya line of a putative Earth-sized planet orbiting in the HZ of the M dwarf GJ436. We estimated the transit depth in the Lya line for an exo-Earth with three types of atmospheres: a hydrogen-dominated atmosphere, a nitrogen-dominated atmosphere, and a nitrogen-dominated atmosphere with an amount of hydrogen equal to that of the Earth. We calculated the in-transit absorption they would produce in the Lya line. We applied it to the out-of-transit Lya observations of GJ 436 obtained by the HST and compared the calculated in-transit absorption with observat…
We present novel, analytical, equilibrium-chemistry formulae for the abundances of molecules in hot exoplanetary atmospheres that include the carbon, oxygen and nitrogen networks. Our hydrogen-dominated solutions involve acetylene (C$_2$H$_2$), ammonia (NH$_3$), carbon dioxide (CO$_2$), carbon monoxide (CO), ethylene (C$_2$H$_4$), hydrogen cyanide (HCN), methane (CH$_4$), molecular nitrogen (N$_2$) and water (H$_2$O). By considering only the gas phase, we prove that the mixing ratio of carbon monoxide is governed by a decic equation (polynomial equation of degree 10). We validate our solutions…
Clouds are ubiquitous\, -- \,they arise for every solar system planet that possesses an atmosphere and have also been suggested as a leading mechanism for obscuring spectral features in exoplanet observations. As exoplanet observations continue to improve, there is a need for efficient and general planetary climate models that appropriately handle the possible cloudy atmospheric environments that arise on these worlds. We generate a new 1D radiative-convective terrestrial planet climate model that self-consistently handles patchy clouds through a parameterized microphysical treatment of conden…
One of the desired outcomes of studying exoplanetary atmospheres is to set decisive constraints on exoplanet formation theories. Astronomers often speak of the "metallicity" in broad terms. When modeling the bulk metallicity, workers refer to the elemental iron abundance (Fe/H). By contrast, when exo-atmospheric astronomers speak of the "metallicity" derived from analysing low-resolution Hubble and Spitzer spectrophotometry, they are referring to the elemental abundances of oxygen (O/H), carbon (C/H) and nitrogen (N/H): in decreasing order of importance, since spectra from the Hubble Wide Fiel…
To identify promising exoplanets for atmospheric characterization and to make the best use of observational data, a thorough understanding of their atmospheres is needed. 3D general circulation models (GCMs) are one of the most comprehensive tools available for this task and will be used to interpret observations of temperate rocky exoplanets. Due to parameterization choices made in GCMs, they can produce different results, even for the same planet. Employing four widely-used exoplanetary GCMs -- ExoCAM, LMD-G, ROCKE-3D and the UM -- we continue the TRAPPIST-1 Habitable Atmosphere Intercompari…
The chemical environments of young planets are assumed to be largely influenced by impacts of bodies lingering on unstable trajectories after the dissolution of the protoplanetary disk. We explore the chemical consequences of impacts within the context of reducing planetary atmospheres dominated by carbon monoxide, methane and molecular nitrogen. A terawatt high-power laser was selected in order to simulate the airglow plasma and blast wave surrounding the impactor. The chemical results of these experiments are then applied to a theoretical atmospheric model. The impact simulation results in s…
Carbon, Hydrogen, Nitrogen, Oxygen, Phosphorus and Sulfur (CHNOPS) play key roles in the origin and proliferation of life on Earth. Given the universality of physics and chemistry, not least the ubiquity of water as a solvent and carbon as a backbone of complex molecules, CHNOPS are likely crucial to most habitable worlds. To help guide and inform the search for potentially habitable and ultimately inhabited environments, we begin by summarizing the CHNOPS budget of various reservoirs on Earth, their role in shaping our biosphere, and their origins in the Solar Nebula. We then synthesize our c…
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 …
