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We present an analysis of CO rovibrational emission lines in the 183 infrared spectra of nearby Class II objects obtained with the NIRSPEC instrument on the Keck II telescope over the past two decades. The sample includes a broad range of stellar mass (both T Tauri and Herbig Ae/Be) and disk evolutionary states (from full to debris disks). We find that 53% of the sample has CO rovibrational emission lines present in their spectrum with disk/stellar subtype detection rates of 82% for transition disks, 61% for Herbigs, and 77% for classical T Tauri stars. Although there is no discernible difference between T Tauri and Herbig Ae/Be star CO detection rates, the detection of accretion and of CO are statistically correlated in T Tauri stars but not in Herbig Ae/Be objects. Within the sample of T Tauri stars, we find that no weak-line T Tauri stars have CO rovibrational emission lines. We use slab modeling to analyze the density, temperature, and emitting area of the sample. The retrieval results imply that Herbig Ae/Be objects tend to have cooler and larger CO emitting regions than T Tauri stars. We find that the CO emitting area is not a thin ring as defined by temperature, but a ring of varying size, likely dependent on the structure of the disk. We also present guidelines on how to approach CO rovibrational emission lines in JWST spectra and present methods for linking ground-based observations with JWST spectra. This includes line-to-continuum ratio estimates based on stellar mass and accretion rate. 

Abstract The ~5 Myr PDS 70 is the only known system with protoplanets residing in the cavity of the circumstellar disk from which they formed, ideal for studying exoplanet formation and evolution within its natal environment. Here, we report the first spin constraint and C/O measurement of PDS 70b from Keck/KPIC high-resolution spectroscopy. We detected CO (3.8σ) and H₂O (3.5σ) molecules in the PDS 70b atmosphere via cross correlation, with a combined CO and H₂O template detection significance of 4.2σ. Our forward-model fits, using BT-Settl model grids, provide an upper limit for the spin rate of PDS 70b (<29 km s⁻¹). The atmospheric retrievals constrain the PDS 70b C/O ratio to ${0.28}_{-0.12}^{+0.20}$(<0.63 under 95% confidence level) and a metallicity [C/H] of ${-0.2}_{-0.5}^{+0.8}$dex, consistent with that of its host star. The following scenarios can explain our measured C/O of PDS 70b in contrast with that of the gas-rich outer disk (for which C/O ≳ 1). First, the bulk composition of PDS 70b might be dominated by dust+ice aggregates rather than disk gas. Another possible explanation is that the disk became carbon enrichedafterPDS 70b was formed, as predicted in models of disk chemical evolution and as observed in both very low-mass stars and older disk systems with JWST/MIRI. Because PDS 70b continues to accrete and its chemical evolution is not yet complete, more sophisticated modeling of the planet and the disk, and higher-quality observations of PDS 70b (and possibly PDS 70c), are necessary to validate these scenarios. 

Abstract We explore terrestrial planet formation with a focus on the supply of solid-state organics as the main source of volatile carbon. For the water-poor Earth, the water ice line, or ice sublimation front, within the planet-forming disk has long been a key focal point. We posit that the soot line, the location where solid-state organics are irreversibly destroyed, is also a key location within the disk. The soot line is closer to the host star than the water snow line and overlaps with the location of the majority of detected exoplanets. In this work, we explore the ultimate atmospheric composition of a body that receives a major portion of its materials from the zone between the soot line and water ice line. We model a silicate-rich world with 0.1% and 1% carbon by mass with variable water content. We show that as a result of geochemical equilibrium, the mantle of these planets would be rich in reduced carbon but have relatively low water (hydrogen) content. Outgassing would naturally yield the ingredients for haze production when exposed to stellar UV photons in the upper atmosphere. Obscuring atmospheric hazes appear common in the exoplanetary inventory based on the presence of often featureless transmission spectra. Such hazes may be powered by the high volatile content of the underlying silicate-dominated mantle. Although this type of planet has no solar system counterpart, it should be common in the galaxy with potential impact on habitability. 

Abstract We present the projected rotational velocity and molecular abundances for HD 33632 Ab obtained via Keck Planet Imager and Characterizer (KPIC) high-resolution spectroscopy. HD 33632 Ab is a nearby benchmark brown dwarf companion at a separation of ∼20 au that straddles the L–T transition. Using a forward-modeling framework with on-axis host star spectra, which provides self-consistent substellar atmospheric and retrieval models for HD 33632 Ab, we derive a projected rotational velocity of 53 ± 3 km s⁻¹and carbon monoxide and water mass fractions of logCO = −2.3 ± 0.3 and logH₂O = −2.7 ± 0.2, respectively. The inferred carbon-to-oxygen ratio (C/O = 0.58 ± 0.14), molecular abundances, and metallicity ([C/H] = 0.0 ± 0.2 dex) of HD 33632 Ab are consistent with its host star. Although detectable methane opacities are expected in L–T transition objects, we did not recover methane in our KPIC spectra, partly due to the highvsiniand to disequilibrium chemistry at the pressures to which we are sensitive. We parameterize the spin as the ratio of rotation to the breakup velocity, and compare HD 33632 Ab to a compilation of >200 very low-mass objects (M≲ 0.1M_⊙) that have spin measurements in the literature. There appears to be no clear trend for the isolated low-mass field objects versus mass, but a tentative trend is identified for low-mass companions and directly imaged exoplanets, similar to previous findings. A larger sample of close-in gas giant exoplanets and brown dwarfs will critically examine our understanding of their formation and evolution through rotation and chemical abundance measurements. 

Abstract Young, self-luminous super-Jovian companions discovered by direct imaging provide a challenging test for planet formation and evolution theories. By spectroscopically characterizing the atmospheric compositions of these super-Jupiters, we can constrain their formation histories. Here we present studies of the recently discovered HIP 99770 b, a 16M_Juphigh-contrast companion on a 17 au orbit, using the fiber-fed high-resolution spectrograph KPIC ( $\mathcal{R}$∼ 35,000) on the Keck II telescope. OurK-band observations led to detections of H₂O and CO in the atmosphere of HIP 99770 b. We carried out free retrieval analyses usingpetitRADTRANSto measure its chemical abundances, including the metallicity and C/O ratio, projected rotation velocity ( $v\sin i$), and radial velocity (RV). We found that the companion’s atmosphere has C/O $={0.55}_{-0.04}^{+0.06}$and [M/H] $={0.26}_{-0.23}^{+0.24}$(1σconfidence intervals), values consistent with those of the Sun and with a companion formation via gravitational instability or core accretion. The projected rotation velocity $v\sin \left(i\right)<7.8$km s⁻¹is small relative to other directly imaged companions with similar masses and ages. This may imply a nearly pole-on orientation or effective magnetic braking by a circumplanetary disk. In addition, we added the companion-to-primary relative RV measurement to the orbital fitting and obtained updated constraints on orbital parameters. Detailed characterization of super-Jovian companions within 20 au like HIP 99770 b is critical for understanding the formation histories of this population. 

Two-dimensional Raman and hybrid terahertz-Raman spectroscopic techniques provide invaluable insight into molecular structures and dynamics of condensed-phase systems. However, corroborating experimental results with theory is difficult due to the high computational cost of incorporating quantum-mechanical effects in the simulations. Here, we present the equilibrium–nonequilibrium ring-polymer molecular dynamics (RPMD), a practical computational method that can account for nuclear quantum effects on the two-time response function of nonlinear optical spectroscopy. Unlike a recently developed approach based on the double Kubo transformed (DKT) correlation function, our method is exact in the classical limit, where it reduces to the established equilibrium-nonequilibrium classical molecular dynamics method. Using benchmark model calculations, we demonstrate the advantages of the equilibrium–nonequilibrium RPMD over classical and DKT-based approaches. Importantly, its derivation, which is based on the nonequilibrium RPMD, obviates the need for identifying an appropriate Kubo transformed correlation function and paves the way for applying real-time path-integral techniques to multidimensional spectroscopy.