Abstract: JWST has created a new era of terrestrial exoplanet atmospheric characterization, and with it, the possibility to detect potential biosignature gases like CH4. Our interpretation of exoplanet atmospheric spectra, and the veracity of these interpretations, will be limited by our understanding of atmospheric processes and the accuracy of input modeling data. Molecular cross sections are essential inputs to these models. The photochemistry of temperate planets depends on photolysis reactions whose rates are governed by the dissociation cross sections of key molecules. H2O is one such molecule; the photolysis of H2O produces OH, a highly reactive and efficient sink for atmospheric trace gases. We investigate the photochemical effects of improved H2O cross sections on anoxic terrestrial planets as a function of host star spectral type and CH4 surface flux. Our results show that updated H2O cross sections, extended to wavelengths >200 nm, substantially impact the predicted abundances of trace gases destroyed by OH. The differences for anoxic terrestrial planets orbiting Sun-like host stars are greatest, showing changes of up to 3 orders of magnitude in surface CO levels, and over an order of magnitude in surface CH4 levels. These differences lead to observable changes in simulated planetary spectra, especially important in the context of future direct-imaging missions. In contrast, the atmospheres of planets orbiting M-dwarf stars are substantially less affected. Our results demonstrate a pressing need for refined dissociation cross-section data for H2O, where uncertainties remain, and other key molecules, especially at mid-UV wavelengths >200 nm.

We present a study of the photochemistry of abiotic habitable planets with anoxic CO$_2$-N$_2$ atmospheres. Such worlds are representative of early Earth, Mars and Venus, and analogous exoplanets. H$_2$O photodissociation controls the atmospheric photochemistry of these worlds through production of reactive OH, which dominates the removal of atmospheric trace gases. The near-UV (NUV; $>200$ nm) absorption cross-sections of H$_2$O play an outsized role in OH production; these cross-sections were heretofore unmeasured at habitable temperatures ($<373$ K). We present the first measurements of NUV H$_2$O absorption at $292$ K, and show it to absorb orders of magnitude more than previously assumed. To explore the implications of these new cross-sections, we employ a photochemical model; we first intercompare it with two others and resolve past literature disagreement. The enhanced OH production due to these higher cross-sections leads to efficient recombination of CO and O$_2$, suppressing both by orders of magnitude relative to past predictions and eliminating the low-outgassing "false positive" scenario for O$_2$ as a biosignature around solar-type stars. Enhanced [OH] increases rainout of reductants to the surface, relevant to prebiotic chemistry, and may also suppress CH$_4$ and H$_2$; the latter depends on whether burial of reductants is inhibited on the underlying planet, as is argued for abiotic worlds. While we focus on CO$_2$-rich worlds, our results are relevant to anoxic planets in general. Overall, our work advances the state-of-the-art of photochemical models by providing crucial new H$_2$O cross-sections and resolving past disagreement in the literature, and suggests that detection of spectrally active trace gases like CO in rocky exoplanet atmospheres may be more challenging than previously considered.

Abstract: Efforts to spectrally characterize the atmospheric compositions of temperate terrestrial exoplanets orbiting M dwarf stars with JWST are now underway. Key molecular targets of such searches include O2 and CO, which are potential indicators of life. Recently, it was proposed that CO2 photolysis generates abundant (≳0.1 bar) abiotic O2 and CO in the atmospheres of habitable M dwarf planets with CO2-rich atmospheres, constituting a strong false positive for O2 as a biosignature and further complicating efforts to use CO as a diagnostic of surface biology. Importantly, this implied that TRAPPIST-1e and TRAPPIST-1f, now under observation with JWST, would abiotically accumulate abundant O2 and CO, if habitable. Here, we use a multi-model approach to reexamine photochemical O2 and CO accumulation on planets orbiting M dwarf stars. We show that photochemical O2 remains a trace gas on habitable CO2-rich M dwarf planets, with earlier predictions of abundant O2 and CO due to an atmospheric model top that was too low to accurately resolve the unusually high CO2 photolysis peak on such worlds. Our work strengthens the case for O2 as a biosignature gas, and affirms the importance of CO as a diagnostic of photochemical O2 production. However, observationally relevant false-positive potential remains, especially for O2's photochemical product O3, and further work is required to confidently understand O2 and O3 as biosignature gases on M dwarf planets.