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Atmospheric observations of mini-Neptunes orbiting M-dwarfs are beginning to provide constraints on their chemical and thermal properties, while also providing clues about their interiors and potential surfaces. With their relatively large scale heights and large planet-star contrasts, mini-Neptunes are currently ideal targets towards the goal of characterising temperate low-mass exoplanets. Understanding the thermal structures and spectral appearances of mini-Neptunes is important to understand various aspects of their atmospheres, including radiative/convective energy transport, boundary conditions for the interior, and their potential habitability. In the present study, we explore these aspects of mini-Neptunes using self-consistent models of their atmospheres. We begin by exploring the effects of irradiation, internal flux, metallicity, clouds and hazes on the atmospheric temperature profiles and thermal emission spectra of temperate mini-Neptunes. In particular, we investigate the impact of these properties on the radiative-convective boundary and the thermodynamic conditions in the lower atmosphere, which serves as the interface with the interior and/or a potential surface. Building on recent suggestions of habitability of the mini-Neptune K2-18 b, we find a range of physically-motivated atmospheric conditions that allow for liquid water under the H_2-rich atmospheres of such planets. We find that observations of thermal emission with JWST/MIRI spectrophotometry can place useful constraints on the habitability of temperate mini-Neptunes such as K2-18 b, and provide more detailed constraints on the chemical and thermal properties of warmer planets such as GJ 3470 b. Our results underpin the potential of temperate mini-Neptunes such as K2-18 b as promising candidates in the search for habitable exoplanets.

Ultra hot jupiters (UHJs), giant exoplanets with equilibrium temperatures above 2000 K, are ideal laboratories for studying metal compositions of planetary atmospheres. At these temperatures the thermal dissociation of metal-rich molecules into their constituent elements makes these atmospheres conducive for elemental characterisation. Several elements, mostly ionized metals, have been detected in UHJs recently using high resolution transit spectroscopy. Even though a number of neutral transition metals (e.g., Fe, Ti, V, Cr) are expected to be strong sources of optical/NUV opacity and, hence, influence radiative processes in the lower atmospheres of UHJs, only Fe I has been detected to date. We conduct a systematic search for atomic species in the UHJ WASP-121 b. Using theoretical models we present a metric to predict the atomic species likely to be detectable in such planets with high resolution transmission spectroscopy. We search for the predicted species in observations of WASP-121 b and report the first detections of neutral transition metals Cr I and V I in an exoplanet at 3.6 $\sigma$ and 4.5 $\sigma$, respectively. We confirm previous detections of Fe I and Fe II. Whereas Fe II was detected previously in the NUV, we detect it in the optical. We infer that the neutral elements Fe I, V I, and Cr I are present in the lower atmosphere, as predicted by thermochemical equilibrium, while Fe II is a result of photoionisation in the upper atmosphere. Our study highlights the rich chemical diversity of UHJs.

© 2017. The American Astronomical Society. All rights reserved. Detecting the atmospheres of low-mass, low-temperature exoplanets is a high-priority goal on the path to ultimately detecting biosignatures in the atmospheres of habitable exoplanets. High-precision HST observations of several super-Earths with equilibrium temperatures below 1000 K have to date all resulted in featureless transmission spectra, which have been suggested to be due to high-altitude clouds. We report the detection of an atmospheric feature in the atmosphere of a 1.6 M⊕ transiting exoplanet, GJ 1132 b, with an equilibrium temperature of ∼600 K and orbiting a nearby M dwarf. We present observations of nine transits of the planet obtained simultaneously in the griz and JHK passbands. We find an average radius of 1.43 ±0.16 R⊕ for the planet, averaged over all the passbands, and a radius of 0.255 ±0.023 R⊙for the star, both of which are significantly greater than previously found. The planet radius can be decomposed into a "surface radius" at ∼1.375 R⊕ overlaid by atmospheric features that increase the observed radius in the z and K bands. The z-band radius is 4σ higher than the continuum, suggesting a strong detection of an atmosphere. We deploy a suite of tests to verify the reliability of the transmission spectrum, which are greatly helped by the existence of repeat observations. The large z-band transit depth indicates strong opacity from H2O and/or CH4 or a hitherto-unconsidered opacity. A surface radius of 1.375 ±0.16 R⊕ allows for a wide range of interior compositions ranging from a nearly Earth-like rocky interior, with ∼70% silicate and ∼30% Fe, to a substantially H2O-rich water world.

We present a high precision H-band emission spectrum of the transiting brown dwarf KELT-1b, which we spectrophotometrically observed during a single secondary eclipse using the LUCI1 multi-object spectrograph on the Large Binocular Telescope. Using a Gaussian-process regression model, we are able to clearly measure the broadband eclipse depth as Delta-H=1418+/-94ppm. We are also able to spectrally-resolve the H-band into five separate wavechannels and measure the eclipse spectrum of KELT-1b at R~50 with an average precision of +/-135ppm. We find that the day side has an average brightness temperature of 3250+/-50K, with significant variation as a function of wavelength. Based on our observations, and previous measurements of KELT-1b's eclipse at other wavelengths, we find that KELT-1b's day side appears identical to an isolated 3200K brown dwarf, and our modeling of the atmospheric emission shows a monotonically decreasing temperature-pressure profile. This is in contrast to hot Jupiters with similar day side brightness temperatures near 3000K, all of which appear to be either isothermal or posses a stratospheric temperature inversion. We hypothesize that the lack of an inversion in KELT-1b is due to its high surface gravity, which we argue could be caused by the increased efficiency of cold-trap processes within its atmosphere.

Broad absorption signatures from alkali metals, such as the sodium (Na I) and potassium (K I) resonance doublets, have long been predicted in the optical atmospheric spectra of cloud-free irradiated gas giant exoplanets1-3. However, observations have revealed only the narrow cores of these features rather than the full pressure-broadened profiles4-6. Cloud and haze opacity at the day-night planetary terminator are considered to be responsible for obscuring the absorption-line wings, which hinders constraints on absolute atmospheric abundances7-9. Here we report an optical transmission spectrum for the 'hot Saturn' exoplanet WASP-96b obtained with the Very Large Telescope, which exhibits the complete pressure-broadened profile of the sodium absorption feature. The spectrum is in excellent agreement with cloud-free, solar-abundance models assuming chemical equilibrium. We are able to measure a precise, absolute sodium abundance of logεNa = [Formula: see text], and use it as a proxy for the planet's atmospheric metallicity relative to the solar value (Zp/Zʘ = [Formula: see text]). This result is consistent with the mass-metallicity trend observed for Solar System planets and exoplanets10-12.

Recent detections of thermal inversions in the dayside atmospheres of some hot Jupiters are motivating new avenues to understand the interplay between their temperature structures and other atmospheric conditions. In particular, TiO has long been proposed to cause thermal inversions in hot Jupiters, depending on other factors such as stellar irradiation, C/O, and vertical mixing. TiO also has spectral features in the optical and near-infrared that have been detected. However, interpretations of TiO signatures rely on the accuracy of TiO opacity used in the models. The recently reported Toto TiO line list provides a new opportunity to investigate these dependencies, which is the goal of the present work. First, we investigate how the Toto line list affects observable transmission and emission spectra of hot Jupiters at low and high resolution. The improvement in the Toto line list compared to a previous line list results in observable differences in the model spectra, particularly in the optical at high resolution. Secondly, we explore the interplay between temperature structure, irradiation and composition with TiO as the primary source of optical opacity, using 1D self-consistent atmospheric models. Among other trends, we find that the propensity for thermal inversions due to TiO peaks at C/O$\sim$0.9, consistent with recent studies. Using these models, we further assess metrics to quantify thermal inversions due to TiO, compared to frequently-used Spitzer photometry, over a range in C/O, irradiation, metallicity, gravity and stellar type.

We present an optical-to-infrared transmission spectrum of the inflated sub-Saturn KELT-11b measured with the Transiting Exoplanet Survey Satellite (TESS), the Hubble Space Telescope (HST) Wide Field Camera 3 G141 spectroscopic grism, and the Spitzer Space Telescope (Spitzer) at 3.6 $\mu$m, in addition to a Spitzer 4.5 $\mu$m secondary eclipse. The precise HST transmission spectrum notably reveals a low-amplitude water feature with an unusual shape. Based on free retrieval analyses with varying molecular abundances, we find strong evidence for water absorption. Depending on model assumptions, we also find tentative evidence for other absorbers (HCN, TiO, and AlO). The retrieved water abundance is generally $\lesssim 0.1\times$ solar (0.001--0.7$\times$ solar over a range of model assumptions), several orders of magnitude lower than expected from planet formation models based on the solar system metallicity trend. We also consider chemical equilibrium and self-consistent 1D radiative-convective equilibrium model fits and find they too prefer low metallicities ($[M/H] \lesssim -2$, consistent with the free retrieval results). However, all the retrievals should be interpreted with some caution since they either require additional absorbers that are far out of chemical equilibrium to explain the shape of the spectrum or are simply poor fits to the data. Finally, we find the Spitzer secondary eclipse is indicative of full heat redistribution from KELT-11b's dayside to nightside, assuming a clear dayside. These potentially unusual results for KELT-11b's composition are suggestive of new challenges on the horizon for atmosphere and formation models in the face of increasingly precise measurements of exoplanet spectra.

We investigate a new class of habitable planets composed of water-rich interiors with massive oceans underlying H2-rich atmospheres, referred to here as Hycean worlds. With densities between those of rocky super-Earths and more extended mini-Neptunes, Hycean planets can be optimal candidates in the search for exoplanetary habitability and may be abundant in the exoplanet population. We investigate the bulk properties (masses, radii, and temperatures), potential for habitability, and observable biosignatures of Hycean planets. We show that Hycean planets can be significantly larger compared to previous considerations for habitable planets, with radii as large as 2.6 Earth radii (2.3 Earth radii) for a mass of 10 Earth masses (5 Earth masses). We construct the Hycean habitable zone (HZ), considering stellar hosts from late M to sun-like stars, and find it to be significantly wider than the terrestrial-like HZ. While the inner boundary of the Hycean HZ corresponds to equilibrium temperatures as high as ~500 K for late M dwarfs, the outer boundary is unrestricted to arbitrarily large orbital separations. Our investigations include tidally locked `Dark Hycean' worlds that permit habitable conditions only on their permanent nightsides and `Cold Hycean' worlds that see negligible irradiation. Finally, we investigate the observability of possible biosignatures in Hycean atmospheres. We find that a number of trace terrestrial biomarkers which may be expected to be present in Hycean atmospheres would be readily detectable using modest observing time with the James Webb Space Telescope (JWST). We identify a sizable sample of nearby potential Hycean planets that can be ideal targets for such observations in search of exoplanetary biosignatures.

Atmospheric retrievals of exoplanetary transmission spectra provide important constraints on various properties such as chemical abundances, cloud/haze properties, and characteristic temperatures, at the day-night atmospheric terminator. To date, most spectra have been observed for giant exoplanets due to which retrievals typically assume H-rich atmospheres. However, recent observations of mini-Neptunes/super-Earths, and the promise of upcoming facilities including JWST, call for a new generation of retrievals that can address a wide range of atmospheric compositions and related complexities. Here we report Aurora, a next-generation atmospheric retrieval framework that builds upon state-of-the-art architectures and incorporates the following key advancements: a) a generalised compositional retrieval allowing for H-rich and H-poor atmospheres, b) a generalised prescription for inhomogeneous clouds/hazes, c) multiple Bayesian inference algorithms for high-dimensional retrievals, d) modular considerations for refraction, forward scattering, and Mie-scattering, and e) noise modeling functionalities. We demonstrate Aurora on current and/or synthetic observations of hot Jupiter HD209458b, mini-Neptune K218b, and rocky exoplanet TRAPPIST1d. Using current HD209458b spectra, we demonstrate the robustness of our framework and cloud/haze prescription against assumptions of H-rich/H-poor atmospheres, improving on previous treatments. Using real and synthetic spectra of K218b, we demonstrate the agnostic approach to confidently constrain its bulk atmospheric composition and obtain precise abundance estimates. For TRAPPIST1d, 10 JWST NIRSpec transits can enable identification of the main atmospheric component for cloud-free CO$_2$-rich and N$_2$-rich atmospheres, and abundance constraints on trace gases including initial indications of O$_3$ if present at enhanced levels ($\sim$10-100x Earth levels).

Optical transmission spectroscopy provides crucial constraints on the reference pressure levels and scattering properties for hot Jupiter atmospheres. For certain planets, where alkali atoms are detected in the atmosphere, their line profiles could serve as a good probe to link upper and lower atmospheric layers. WASP-21b is a Saturn-mass hot Jupiter orbiting a thick disc star, with a low density and an equilibrium temperature of 1333 K, which makes it a good target for transmission spectroscopy. Here, we present a low-resolution transmission spectrum for WASP-21b based in one transit observed by the OSIRIS spectrograph at the 10.4 m Gran Telescopio Canarias (GTC), and a high-resolution transmission spectrum based in three transits observed by HARPS-N at Telescopio Nazinale Galileo (TNG) and HARPS at the ESO 3.6 m telescope. We performed spectral retrieval analysis on GTC's low-resolution transmission spectrum and report the detection of Na at a confidence level of $>$3.5-$\sigma$. The Na line exhibits a broad line profile that can be attributed to pressure broadening, indicating a mostly clear planetary atmosphere. The spectrum shows a tentative excess absorption at the K D$_1$ line. Using HARPS-N and HARPS, we spectrally resolved the Na doublet transmission spectrum. An excess absorption at the Na doublet is detected during the transit, and shows a radial velocity shift consistent with the planet orbital motion. We proposed a metric to quantitatively distinguish hot Jupiters with relatively clear atmospheres from others, and WASP-21b has the largest metric value among all the characterized hot Jupiters. The detection of Na at both lower and upper atmosphere of WASP-21b reveals that it is an ideal target for future follow-up observations, providing the opportunity to understand the nature of its atmosphere across a wide range of pressure levels.

Transmission spectroscopy provides a powerful probe of the atmospheric properties of transiting exoplanets. To date, studies of exoplanets in transit have focused on inferring their atmospheric properties such as chemical compositions, cloud/haze properties, and temperature structures. However, surface inhomogeneities in the host stars of exoplanets in the form of cool spots and hot faculae can in principle imprint signatures on the observed planetary transit spectrum. Here we present Aura, a new retrieval paradigm for inferring both planetary and stellar properties from a transmission spectrum. We apply our retrieval framework to a sample of hot giant exoplanets to determine the significance of stellar heterogeneity and clouds/hazes in their spectra. The retrieval analyses distinguish four groups of planets. First, the spectra of WASP-6b and WASP-39b are best characterised by imprints of stellar heterogeneity and hazes and/or clouds. HD 209458b and HAT-P-12b comprise the second group for which there is weak evidence for stellar heterogeneity and a high significance of hazes and/or clouds. The third group constitutes HAT-P-1b and WASP-31b and shows weak evidence against stellar heterogeneity but weak to substantial indications of clouds/hazes. The fourth group -- WASP-19b, WASP-17b, and WASP-12b -- is fit best by molecular and alkali absorbers with H$_2$ scattering without evidence for stellar heterogeneity and weak to no evidence for clouds/hazes. Our retrieval methodology paves the way to simultaneous information on the star and planet from higher resolution spectra using future facilities such as the James Webb Space Telescope and large ground-based facilities.

Observations of exoplanetary spectra are leading to unprecedented constraints on their atmospheric elemental abundances, particularly O/H, C/H, and C/O ratios. Recent studies suggest that elemental ratios could provide important constraints on formation and migration mechanisms of giant exoplanets. A fundamental assumption in such studies is that the chemical composition of the planetary envelope represents the sum-total of compositions of the accreted gas and solids during the formation history of the planet. We investigate the efficiency with which accreted planetesimals ablate in a giant planetary envelope thereby contributing to its composition rather than sinking to the core. From considerations of aerodynamic drag causing `frictional ablation' and the envelope temperature structure causing `thermal ablation', we compute mass ablations for impacting planetesimals of radii 30 m to 1 km for different compositions (ice to iron) and a wide range of velocities and impact angles, assuming spherical symmetry. Icy impactors are fully ablated in the outer envelope for a wide range of parameters. Even for Fe impactors substantial ablation occurs in the envelope for a wide range of sizes and velocities. For example, iron impactors of sizes below ~0.5 km and velocities above ~30 km/s are found to ablate by ~60-80% within the outer envelope at pressures below 10^3 bar due to frictional ablation alone. For deeper pressures (~10^7 bar), substantial ablation happens over a wider range of parameters. Therefore, our exploratory study suggests that atmospheric abundances of volatile elements in giant planets reflect their accretion history during formation.

High resolution spectroscopy (HRS) has been used to detect a number of species in the atmospheres of hot Jupiters. Key to such detections is accurately and precisely modelled spectra for cross-correlation against the R$\gtrsim$20,000 observations. There is a need for the latest generation of opacities which form the basis for high signal-to-noise detections using such spectra. In this study we present and make publicly available cross sections for six molecular species, H$_2$O, CO, HCN, CH$_4$, NH$_3$ and CO$_2$ using the latest line lists most suitable for low- and high-resolution spectroscopy. We focus on the infrared (0.95-5~$\mu$m) and between 500-1500~K where these species have strong spectral signatures. We generate these cross sections on a grid of pressures and temperatures typical for the photospheres of super Earth, warm Neptunes and hot Jupiters using the latest H$_2$ and He pressure broadening. We highlight the most prominent infrared spectral features by modelling three representative exoplanets, GJ~1214~b, GJ~3470~b and HD~189733~b, which encompass a wide range in temperature, mass and radii. In addition, we verify the line lists for H$_2$O, CO and HCN with previous high resolution observations of hot Jupiters. However, we are unable to detect CH$_4$ with our new cross sections from HRS observations of HD~102195~b. These high accuracy opacities are critical for atmospheric detections with HRS and will be continually updated as new data becomes available.

The alkali metal sodium (Na) is one of the most commonly detected chemical species in the upper atmospheres of giant exoplanets. In this work we conducted a homogeneous survey of Na in a diverse sample of ten highly irradiated giant exoplanets using high-resolution transmission spectroscopy. Our sample includes nine planets with previous Na detections and one new detection. We confirm previous detections and assess multiple approaches for deriving Na line properties from high-resolution transmission spectra. The homogeneously measured sodium line depths were used to constrain the atmospheric heights ($H_{\text{Na}}$) with respect to the planetary radii ($R_{\text{p}}$). We assess an empirical trend describing the relative atmospheric height ($H_{\text{Na}}/R_{\text{p}}$) as a function of planetary equilibrium temperature ($T_{\text{eq}}$) and surface gravity ($g$), in which $H_{\text{Na}}/R_{\text{p}}$ decreases exponentially with $\xi \propto gT_{\text{eq}}$, approaching a constant at large $\xi$. We also report the sodium D2/D1 line ratios across our sample and find that seven targets have line ratios that are consistent with unity. Finally, we measured net blueshifted offsets of the sodium absorption lines from their rest frame wavelengths for all ten planets, corresponding to day-night wind velocities of a few km s$^{-1}$. This suggests that the broad sample of exoplanets share common underlying processes that govern atmospheric dynamics. Our study highlights a promising avenue for using high-resolution transmission spectroscopy to further our understanding of how atmospheric characteristics vary over a diverse sample of exoplanets.

The complexity of atmospheric retrieval models is largely data-driven and one-dimensional models have generally been considered adequate with current data quality. However, recent studies have suggested that using 1D models in retrievals can result in anomalously cool terminator temperatures and biased abundance estimates even with existing transmission spectra of hot Jupiters. Motivated by these claims and upcoming high-quality transmission spectra we systematically explore the limitations of 1D models using synthetic and current observations. We use 1D models of varying complexity, both analytic and numerical, to revisit claims of biases when interpreting transmission spectra of hot Jupiters with inhomogeneous terminator compositions. Overall, we find the reported biases to be resulting from specific model assumptions rather than intrinsic limitations of 1D atmospheric models in retrieving current observations of asymmetric terminators. Additionally, we revise atmospheric retrievals of the hot Jupiter WASP-43b ($T_{\rm eq}=1440$ K) and the ultra-hot Jupiter WASP-103b ($T_{\rm eq}=2484$ K ) for which previous studies inferred abnormally cool atmospheric temperatures. We retrieve temperatures consistent with expectations. We note, however, that in the limit of extreme terminator inhomogeneities and high data quality some atmospheric inferences may conceivably be biased, although to a lesser extent than previously claimed. To address such cases, we implement a 2D retrieval framework for transmission spectra which allows accurate constraints on average atmospheric properties and provides insights into the spectral ranges where the imprints of atmospheric inhomogeneities are strongest. Our study highlights the need for careful considerations of model assumptions and data quality before attributing biases in retrieved estimates to unaccounted atmospheric inhomogeneities., Replaced with version accepted for publication in The Astrophysical Journal

Understanding the internal structures of planets with a large H$_2$O component is important for the characterisation of sub-Neptune planets. The finding that the mini-Neptune K2-18b could host a liquid water ocean beneath a mostly hydrogen envelope motivates a detailed examination of the phase structures of water-rich planets. To this end, we present new internal structure models for super-Earths and mini-Neptunes that enable detailed characterisation of a planet's water component. We use our models to explore the possible phase structures of water worlds and find that a diverse range of interiors are possible, from oceans sandwiched between two layers of ice to supercritical interiors beneath steam atmospheres. We determine how the bulk properties and surface conditions of a water world affect its ocean depth, finding that oceans can be up to hundreds of times deeper than on Earth. For example, a planet with a 300 K surface can possess H$_2$O oceans with depths from 30-500 km, depending on its mass and composition. We also constrain the region of mass-radius space in which planets with H/He envelopes could host liquid H$_2$O, noting that the liquid phase can persist at temperatures up to 647 K at high pressures of $218$-$7\times10^4$ bar. Such H/He envelopes could contribute significantly to the planet radius while retaining liquid water at the surface, depending on the planet mass and temperature profile. Our findings highlight the exciting possibility that habitable conditions may be present on planets much larger than Earth., Comment: 19 pages, 15 figures. Accepted for publication in MNRAS

Atmospheres of a number of ultra-hot Jupiters (UHJs) with temperatures $\gtrsim$2000~K have been observed recently. Many of these planets show largely featureless thermal spectra in the near-infrared observed with the HST WFC3 spectrograph (1.1-1.7~$\mu$m) even though this spectral range contains strong H$_2$O opacity. Recent works have proposed the possibility of H- opacity masking the H$_2$O feature and/or thermal dissociation of H$_2$O causing its apparent depletion at the high temperatures of UHJs. In this work we test these hypotheses using observations of the exoplanet WASP-18b as a case study. We report detailed atmospheric retrievals of the planet using the HyDRA retrieval code, extended to include the effects of H- opacity and thermal dissociation. We report constraints on the H$_2$O, CO and H- abundances as well as the pressure-temperature profile of the dayside atmosphere for retrievals with and without H-/dissociation for each dataset. We find that the H$_2$O and H- abundances are relatively unconstrained given the featureless WFC3 spectra. We do not conclusively detect H- in the planet contrary to previous studies which used equilibrium models to infer its presence. The constraint on the CO abundance depends on the combination of WFC3 and Spitzer data, ranging from solar to super-solar CO values. We additionally see signs of a thermal inversion from two of the datasets. Our study demonstrates the potential of atmospheric retrievals of UHJs including the effects of H- and thermal dissociation of molecules., Comment: 19 pages, 10 figures, accepted for publication in The Astronomical Journal

Inferences of molecular compositions of exoplanetary atmospheres have generally focused on C, H, and O-bearing molecules. Recently, additional absorption in HST WFC3 transmission spectra around 1.55$\mu$m has been attributed to nitrogen-bearing chemical species: NH$_3$ or HCN. These species, if present in significant abundance, would be strong indicators of disequilibrium chemical processes -- e.g. vertical mixing and photochemistry. The derived N abundance, in turn, could also place important constraints on planetary formation mechanisms. Here, we examine the detectability of nitrogen chemistry in exoplanetary atmospheres. In addition to the WFC3 bandpass (1.1-1.7$\mu$m), we find that observations in K-band at $\sim$2.2$\mu$m, achievable with present ground-based telescopes, sample a strong NH$_3$ feature, whilst observations at $\sim$3.1$\mu$m and $\sim$4.0$\mu$m sample strong HCN features. In anticipation of such observations, we predict absorption feature amplitudes due to nitrogen chemistry in the 1-5$\mu$m spectral range possible for a typical hot Jupiter. Finally, we conduct atmospheric retrievals of 9 hot Jupiter transmission spectra in search of near-infrared absorption features suggestive of nitrogen chemistry. We report weak detections of NH$_3$ in WASP-31b (2.2$\sigma$), HCN in WASP-63b (2.3$\sigma$), and excess absorption that could be attributed to NH$_3$ in HD 209458b. High-precision observations from 1-5$\mu$m (e.g., with the James Webb Space Telescope), will enable definitive detections of nitrogen chemistry, in turn serving as powerful diagnostics of disequilibrium atmospheric chemistry and planetary formation processes., Comment: 9 pages, 5 figures. Accepted for publication in ApJL