A data resource for prediction of gas-phase thermodynamic properties of small molecules

The thermodynamic properties of a substance are key to predicting its behavior in physical and chemical systems. Specifically, the enthalpy of formation and entropy of a substance can be used to predict whether reactions involving that substance will proceed spontaneously under conditions of constant temperature and pressure, and if they do, what the heat and work yield of those reactions would be. Prediction of enthalpy and entropy of substances is therefore of value for substances for which those parameters have not been experimentally measured. We developed a database of 2869 experimental values of enthalpy of formation and 1403 values for entropy for substances composed of stable small molecules, derived from the literature. We developed a model for predicting enthalpy of formation and entropy from semiempirical quantum mechanical calculations of energy and atom counts, and applied the model to a comprehensive database of 16,417 small molecules. The database of small-molecule thermodynamic properties will be useful for predicting the outcome of any process that might involve the generation or destruction of volatile products, such as atmospheric chemistry, volcanism, or waste pyrolysis. Additionally, the collected experimental thermodynamic values will be of value to others developing models to predict enthalpy and entropy

Phosphine as a Biosignature Gas in Exoplanet Atmospheres

A long-term goal of exoplanet studies is the identification and detection of biosignature gases. Beyond the most discussed biosignature gas O₂, only a handful of gases have been considered in detail. In this study, we evaluate phosphine (PH₃). On Earth, PH₃ is associated with anaerobic ecosystems, and as such, it is a potential biosignature gas in anoxic exoplanets. We simulate the atmospheres of habitable terrestrial planets with CO₂- and H₂-dominated atmospheres and find that PH₃ can accumulate to detectable concentrations on planets with surface production fluxes of 10¹⁰ to 10¹⁴ cm⁻² s⁻¹ (corresponding to surface concentrations of 10s of ppb to 100s of ppm), depending on atmospheric composition and ultraviolet (UV) irradiation. While high, the surface flux values are comparable to the global terrestrial production rate of methane or CH₄ (10¹¹ cm⁻² s⁻¹) and below the maximum local terrestrial PH₃ production rate (10¹⁴ cm⁻² s⁻¹). As with other gases, PH₃ can more readily accumulate on low-UV planets, for example, planets orbiting quiet M dwarfs or with a photochemically generated UV shield. PH₃ has three strong spectral features such that in any atmosphere scenario one of the three will be unique compared with other dominant spectroscopic molecules. Phosphine's weakness as a biosignature gas is its high reactivity, requiring high outgassing rates for detectability. We calculate that tens of hours of JWST (James Webb Space Telescope) time are required for a potential detection of PH₃. Yet, because PH₃ is spectrally active in the same wavelength regions as other atmospherically important molecules (such as H₂O and CH₄), searches for PH₃ can be carried out at no additional observational cost to searches for other molecular species relevant to characterizing exoplanet habitability. Phosphine is a promising biosignature gas, as it has no known abiotic false positives on terrestrial planets from any source that could generate the high fluxes required for detection

Assessment of Isoprene as a Possible Biosignature Gas in Exoplanets with Anoxic Atmospheres

Research for possible biosignature gases on habitable exoplanet atmosphere is accelerating. We add isoprene, C5H8, to the roster of biosignature gases. We found that formation of isoprene geochemical formation is highly thermodynamically disfavored and has no known abiotic false positives. The isoprene production rate on Earth rivals that of methane (~ 500 Tg yr-1). On Earth, isoprene is rapidly destroyed by oxygen-containing radicals, but its production is ubiquitous to a diverse array of evolutionarily distant organisms, from bacteria to plants and animals-few, if any at all, volatile secondary metabolite has a larger evolutionary reach. While non-photochemical sinks of isoprene may exist, the destruction of isoprene in an anoxic atmosphere is mainly driven by photochemistry. Motivated by the concept that isoprene might accumulate in anoxic environments, we model the photochemistry and spectroscopic detection of isoprene in habitable temperature, rocky exoplanet anoxic atmospheres with a variety of atmosphere compositions under different host star UV fluxes. Limited by an assumed 10 ppm instrument noise floor, habitable atmosphere characterization using JWST is only achievable with transit signal similar or larger than that for a super-Earth sized exoplanet transiting an M dwarf star with an H2-dominated atmosphere. Unfortunately, isoprene cannot accumulate to detectable abundance without entering a run-away phase, which occurs at a very high production rate, ~ 100 times Earth's production rate. In this run-away scenario isoprene will accumulate to > 100 ppm and its spectral features are detectable with ~ 20 JWST transits. One caveat is that some spectral features are hard to be distinguished from that of methane. Despite these challenges, isoprene is worth adding to the menu of potential biosignature gases.Comment: 62 pages, 24 figure

Stellar Flares from the First TESS Data Release: Exploring a New Sample of M Dwarfs

We perform a study of stellar flares for the 24,809 stars observed with 2 minute cadence during the first two months of the TESS mission. Flares may erode exoplanets' atmospheres and impact their habitability, but might also trigger the genesis of life around small stars. TESS provides a new sample of bright dwarf stars in our galactic neighborhood, collecting data for thousands of M dwarfs that might host habitable exoplanets. Here, we use an automated search for flares accompanied by visual inspection. Then, our public allesfitter code robustly selects the appropriate model for potentially complex flares via Bayesian evidence. We identify 1228 flaring stars, 673 of which are M dwarfs. Among 8695 flares in total, the largest superflare increased the stellar brightness by a factor of 16.1. Bolometric flare energies range from 1031.0 to 1036.9 erg, with a median of 1033.1 erg. Furthermore, we study the flare rate and energy as a function of stellar type and rotation period. We solidify past findings that fast rotating M dwarfs are the most likely to flare and that their flare amplitude is independent of the rotation period. Finally, we link our results to criteria for prebiotic chemistry, atmospheric loss through coronal mass ejections, and ozone sterilization. Four of our flaring M dwarfs host exoplanet candidates alerted on by TESS, for which we discuss how these effects can impact life. With upcoming TESS data releases, our flare analysis can be expanded to almost all bright small stars, aiding in defining criteria for exoplanet habitability

Phosphine on Venus Cannot be Explained by Conventional Processes

The recent candidate detection of ~1 ppb of phosphine in the middle atmosphere of Venus is so unexpected that it requires an exhaustive search for explanations of its origin. Phosphorus-containing species have not been modelled for Venus' atmosphere before and our work represents the first attempt to model phosphorus species in the Venusian atmosphere. We thoroughly explore the potential pathways of formation of phosphine in a Venusian environment, including in the planet's atmosphere, cloud and haze layers, surface, and subsurface. We investigate gas reactions, geochemical reactions, photochemistry, and other non-equilibrium processes. None of these potential phosphine production pathways are sufficient to explain the presence of ppb phosphine levels on Venus. If PH3's presence in Venus' atmosphere is confirmed, it therefore is highly likely to be the result of a process not previously considered plausible for Venusian conditions. The process could be unknown geochemistry, photochemistry, or even aerial microbial life, given that on Earth phosphine is exclusively associated with anthropogenic and biological sources. The detection of phosphine adds to the complexity of chemical processes in the Venusian environment and motivates in situ follow up sampling missions to Venus. Our analysis provides a template for investigation of phosphine as a biosignature on other worlds.Comment: v2 is in press in Astrobiology, Special Collection: Venus; v2 also expands on the potential of phosphides from the deep mantle volcanism as a source of PH3 (as suggested by Truong and Lunine 2021: https://www.pnas.org/content/118/29/e2021689118) and shows the volcanic source of PH3 to be unlikel

Venusian phosphine:a 'Wow!' signal in chemistry?

The potential detection of ppb levels phosphine (PH3) in the clouds of Venus through millimeter-wavelength astronomical observations is extremely surprising as PH3 is an unexpected component of an oxidized environment of Venus. A thorough analysis of potential sources suggests that no known process in the consensus model of Venus' atmosphere or geology could produce PH3 at anywhere near the observed abundance. Therefore, if the presence of PH3 in Venus' atmosphere is confirmed, it is highly likely to be the result of a process not previously considered plausible for Venusian conditions. The source of atmospheric PH3 could be unknown geo- or photochemistry, which would imply that the consensus on Venus' chemistry is significantly incomplete. An even more extreme possibility is that strictly aerial microbial biosphere produces PH3. This paper summarizes the Venusian PH3 discovery and the scientific debate that arose since the original candidate detection one year ago.Comment: A short overview of the Venusian PH3 discovery and the scientific debate that arose since the original candidate detection in September 2020. Additional discussion of possible non-canonical sources of PH3 on Venus is also included. arXiv admin note: text overlap with arXiv:2009.0649

Phosphine on Venus Cannot be Explained by Conventional Processes

The recent candidate detection of ~1 ppb of phosphine in the middle atmosphere of Venus is so unexpected that it requires an exhaustive search for explanations of its origin. Phosphorus-containing species have not been modelled for Venus' atmosphere before and our work represents the first attempt to model phosphorus species in the Venusian atmosphere. We thoroughly explore the potential pathways of formation of phosphine in a Venusian environment, including in the planet's atmosphere, cloud and haze layers, surface, and subsurface. We investigate gas reactions, geochemical reactions, photochemistry, and other non-equilibrium processes. None of these potential phosphine production pathways are sufficient to explain the presence of ppb phosphine levels on Venus. If PH3's presence in Venus' atmosphere is confirmed, it therefore is highly likely to be the result of a process not previously considered plausible for Venusian conditions. The process could be unknown geochemistry, photochemistry, or even aerial microbial life, given that on Earth phosphine is exclusively associated with anthropogenic and biological sources. The detection of phosphine adds to the complexity of chemical processes in the Venusian environment and motivates in situ follow up sampling missions to Venus. Our analysis provides a template for investigation of phosphine as a biosignature on other worlds.Comment: v2 is in press in Astrobiology, Special Collection: Venus; v2 also expands on the potential of phosphides from the deep mantle volcanism as a source of PH3 (as suggested by Truong and Lunine 2021: https://www.pnas.org/content/118/29/e2021689118) and shows the volcanic source of PH3 to be unlikel