Search

This work aims at providing fundamental general tools for the analysis of water spectra as observed in protoplanetary disks with JWST-MIRI. We analyze 25 high-quality spectra from the JDISC Survey reduced with asteroid calibrators as presented in Pontoppidan et al. 2024. First, we present a spectral atlas to illustrate the clustering of water transitions from different upper level energies ($E_u$) and identify single (un-blended) lines that provide the most reliable measurements. With the atlas, we demonstrate two important excitation effects: one related to the opacity saturation of ortho-para line pairs that overlap, and the other to the sub-thermal excitation of $v=1-1$ lines scattered across the $v=0-0$ rotational band. Second, from this larger line selection we define a list of fundamental lines spanning $E_u$ from 1500 to 6000 K to develop simple line-ratio diagrams as diagnostics of temperature components and column density. Third, we report the detection of disk-rotation Doppler broadening of molecular lines, which demonstrates the radial distribution of water emission at different $E_u$ and confirms from gas kinematics a radially-extended $\approx 170$--220 K reservoir, close to the ice sublimation front. We also report the detection of narrow blue-shifted absorption from an inner disk wind in ro-vibrational H2O and CO lines, which may be observed in disks at inclinations $> 50$ deg. We summarize these findings and tools into a general recipe that should be beneficial to community efforts to study water in planet-forming regions., Comment: Community input and feedback is very welcome. Referee report received and asking for minor revisions. Some analysis updates are in progress. The rest of the sample in Appendix H will be included later

The mid-infrared water vapor emission spectrum provides a novel way to characterize the delivery of icy pebbles towards the innermost ($<5$ au) regions of planet-forming disks. Recently, JWST MIRI-MRS showed that compact disks exhibit an excess of low-energy water vapor emission relative to extended multi-gapped disks, suggesting that icy pebble drift is more efficient in the former. We carry out detailed emission line modeling to retrieve the excitation conditions of rotational water vapor emission in a sample of four compact and three extended disks within the JDISC Survey. We present two-temperature H$_2$O slab model retrievals and, for the first time, constrain the spatial distribution of water vapor by fitting parametric radial temperature and column density profiles. Such models statistically outperform the two-temperature slab fits. We find a correlation between the observable hot water vapor mass and stellar mass accretion rate, as well as an anti-correlation between cold water vapor mass and sub-mm dust disk radius, confirming previously reported water line flux trends. We find that the mid-IR spectrum traces H$_2$O with temperatures down to 180-300 K, but the coldest 150-170 K gas remains undetected. Furthermore the H$_2$O temperature profiles are generally steeper and cooler than the expected `super-heated' dust temperature in passive irradiated disks. The column density profiles are used to estimate icy pebble mass fluxes, which suggest that compact and extended disks may produce markedly distinct inner-disk exoplanet populations if local feeding mechanisms dominate their assembly., Comment: Accepted for publication in ApJ

GQ Lup B is one of the few substellar companions with a detected cicumplanetary disk, or CPD. Observations of the CPD suggest the presence of a cavity, possibly formed by an exo-satellite. Using the Keck Planet Imager and Characterizer (KPIC), a high contrast imaging suite that feeds a high resolution spectrograph (1.9-2.5 microns, R$\sim$35,000), we present the first dedicated radial velocity (RV) observations around a high-contrast, directly imaged substellar companion, GQ Lup B, to search for exo-satellites. Over 11 epochs, we find a best and median RV error of 400-1000 m/s, most likely limited by systematic fringing in the spectra due to transmissive optics within KPIC. With this RV precision, KPIC is sensitive to exomoons 0.6-2.8% the mass of GQ Lup B ($\sim 30 M_{\text{Jup}}$) at separations between the Roche limit and $65 R_{\text{Jup}}$, or the extent of the cavity inferred within the CPD detected around GQ Lup B. Using simulations of HISPEC, a high resolution infrared spectrograph planned to debut at W.M. Keck Observatory in 2026, we estimate future exomoon sensitivity to increase by over an order of magnitude, providing sensitivity to less massive satellites potentially formed within the CPD itself. Additionally, we run simulations to estimate the amount of material that different masses of satellites could clear in a CPD to create the observed cavity. We find satellite-to-planet mass ratios of $q > 2 \times 10^{-4}$ can create observable cavities and report a maximum cavity size of $\sim 51 \, R_{\text{Jup}}$ carved from a satellite., Comment: 15 pages, 5 figures

The Keck Planet Imager and Characterizer (KPIC) combines high contrast imaging with high resolution spectroscopy (R$\sim$35,000 in K band) to study directly imaged exoplanets and brown dwarfs in unprecedented detail. KPIC aims to spectrally characterize substellar companions through measurements of planetary radial velocities, spins, and atmospheric composition. Currently, the dominant source of systematic noise for KPIC is fringing, or oscillations in the spectrum as a function of wavelength. The fringing signal can dominate residuals by up to 10% of the continuum for high S/N exposures, preventing accurate wavelength calibration, retrieval of atmospheric parameters, and detection of planets with flux ratios less than 1% of the host star. To combat contamination from fringing, we first identify its three unique sources and adopt a physically informed model of Fabry-P\'{e}rot cavities to apply to post-processed data. We find this strategy can effectively model the fringing in observations of A0V/F0V stars, reducing the residual systematics caused by fringing by a factor of 2. Next, we wedge two of the transmissive optics internal to KPIC to eliminate two sources of fringing and confirm the third source as the entrance window to the spectrograph. Finally, we apply our previous model of the Fabry-P\'{e}rot cavity to new data taken with the wedged optics to reduce the amplitude of the residuals by a factor of 10., Comment: 13 pages, 6 figures

Young, self-luminous super-Jovian companions discovered by direct imaging provide a challenging test of 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 16 MJup high-contrast companion on a 17 au orbit, using the fiber-fed high-resolution spectrograph KPIC (R~35,000) on the Keck II telescope. Our K-band observations led to detections of H2O and CO in the atmosphere of HIP 99770 b. We carried out free retrieval analyses using petitRADTRANS to measure its chemical abundances, including the metallicity and C/O ratio, projected rotation velocity (vsini), 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) (1{\sigma} confidence intervals), values consistent with those of the Sun and with a companion formation via gravitational instability or core accretion. The projected rotation velocity < 7.8 km/s is small relative to other directly imaged companions with similar masses and ages. This may imply a near 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., Comment: 18 pages, 5 figures, accepted to AJ

The Keck Planet Imager and Characterizer (KPIC), a series of upgrades to the Keck II Adaptive Optics System and Instrument Suite, aims to demonstrate high-resolution spectroscopy of faint exoplanets that are spatially resolved from their host stars. In this paper, we measure KPIC's sensitivity to companions as a function of separation (i.e., the contrast curve) using on-sky data collected over four years of operation. We show that KPIC is able to reach contrasts of $1.3 \times 10^{-4}$ at 90 mas and $9.2 \times 10^{-6}$ at 420 mas separation from the star, and that KPIC can reach planet-level sensitivities at angular separations within the inner working angle of coronagraphic instruments such as GPI and SPHERE. KPIC is also able to achieve more extreme contrasts than other medium-/high-resolution spectrographs that are not as optimized for high-contrast performance. We decompose the KPIC performance budget into individual noise terms and discuss limiting factors. The fringing that results from combining a high-contrast imaging system with a high-resolution spectrograph is identified as an important source of systematic noise. After mitigation and correction, KPIC is able to reach within a factor of 2 of the photon noise limit at separations < 200 mas. At large separations, KPIC is limited by the background noise performance of NIRSPEC., Comment: 16 pages, 6 figures, submitted to the proceedings of SPIE Astronomical Telescopes + Instrumentation 2024, 13096-69

Using Keck Planet Imager and Characterizer (KPIC) high-resolution ($R$~35000) spectroscopy from 2.29-2.49 $\mu$m, we present uniform atmospheric retrievals for eight young substellar companions with masses of ~10-30 $M_\textrm{Jup}$, orbital separations spanning ~50-360 au, and $T_\textrm{eff}$ between ~1500-2600 K. We find that all companions have solar C/O ratios, and metallicities, to within the 1-2$\sigma$ level, with the measurements clustered around solar composition. Stars in the same stellar associations as our systems have near-solar abundances, so these results indicate that this population of companions is consistent with formation via direct gravitational collapse. Alternatively, core accretion outside the CO snowline would be compatible with our measurements, though the high mass ratios of most systems would require rapid core assembly and gas accretion in massive disks. On a population level, our findings can be contrasted with abundance measurements for directly imaged planets with m<10 $M_\textrm{Jup}$, which show tentative atmospheric metal enrichment. In addition, the atmospheric compositions of our sample of companions are distinct from those of hot Jupiters, which most likely form via core accretion. For two companions with $T_\textrm{eff}$~1700-2000 K (kap And b and GSC 6214-210 b), our best-fit models prefer a non-gray cloud model with >3$\sigma$ significance. The cloudy models yield 2-3$\sigma$ lower $T_\textrm{eff}$ for these companions, though the C/O and [C/H] still agree between cloudy and clear models at the $1\sigma$ level. Finally, we constrain 12CO/13CO for three companions with the highest S/N data (GQ Lup b, HIP 79098 b, and DH Tau b), and report $v$sin($i$) and radial velocities for all companions., Comment: Accepted to ApJ, 52 pages, 20 figures

We present the projected rotational velocity and molecular abundances for HD 33632 Ab obtained via Keck Planet Imager and Characterizer high-resolution spectroscopy. HD 33632 Ab is a nearby benchmark brown dwarf companion at a separation of $\sim$20 au that straddles the L/T transition. Using a forward-modeling framework with on-axis host star spectra, self-consistent substellar atmospheric and retrieval models for HD 33632 Ab, we derive a projected rotational velocity of 53 $\pm$ 3 km/s and carbon/water mass fractions of log CO = $-$2.3 $\pm$ 0.3 and log H$_2$O = $-$2.7 $\pm$ 0.2. The inferred carbon-to-oxygen ratio (C/O = 0.58 $\pm$ 0.14), molecular abundances, and metallicity ([C/H] = 0.0 $\pm$ 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 high $v\sin{i}$ and to disequilibrium chemistry at the pressures we are sensitive to. We parameterize the spin as the ratio of rotation over break-up velocity, and compare HD 33632 Ab to a compilation of >200 very low-mass objects (M$\lesssim$0.1 M$_{\odot}$) that have spin measurements in the literature. There appears to be no clear trend for the isolated field low-mass 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., Comment: Accepted for publication in the Astrophysical Journal. 36 pages, 15 figures, 5 tables

The 1RXS J034231.8+121622 system consists of an M dwarf primary and a directly imaged low-mass stellar companion. We use high resolution spectroscopic data from Keck/KPIC to estimate the objects' atmospheric parameters and radial velocities (RVs). Using PHOENIX stellar models, we find that the primary has a temperature of 3460 $\pm$ 50 K a metallicity of 0.16 $\pm$ 0.04, while the secondary has a temperature of 2510 $\pm$ 50 K and a metallicity of $0.13\substack{+0.12 \\ -0.11}$. Recent work suggests this system is associated with the Hyades, placing it an older age than previous estimates. Both metallicities agree with current $[Fe/H]$ Hyades measurements (0.11 -- 0.21). Using stellar evolutionary models, we obtain significantly higher masses for the objects, of 0.30 $\pm$ 0.15 $M_\odot$ and 0.08 $\pm$ 0.01 $M_\odot$ (84 $\pm$ 11 $M_{Jup}$) respectively. Using the RVs and a new astrometry point from Keck/NIRC2, we find that the system is likely an edge-on, moderately eccentric ($0.41\substack{+0.27 \\ -0.08}$) configuration. We also estimate the C/O ratio of both objects using custom grid models, obtaining 0.42 $\pm$ 0.10 (primary) and 0.55 $\pm$ 0.10 (companion). From these results, we confirm that this system most likely went through a binary star formation process in the Hyades. The significant changes in this system's parameters since its discovery highlight the importance of high resolution spectroscopy for both orbital and atmospheric characterization of directly imaged companions., Comment: 30 pages, 18 figures, accepted for publication in AJ

Molecular emission is used to investigate both the physical and chemical properties of protoplanetary disks. Therefore, to accurately derive disk properties, we need a thorough understanding of the behavior of the molecular probes we rely on. Here we investigate how the molecular line emission of N$_2$H$^+$, HCO$^+$, HCN, and C$^{18}$O compare to other measured quantities in a set of 20 protoplanetary disks. Overall, we find positive correlations between multiple line fluxes and the disk dust mass and radius. We also generally find strong positive correlations between the line fluxes of different molecular species. However, some disks do show noticeable differences in the relative fluxes of N$_2$H$^+$, HCO$^+$, HCN, and C$^{18}$O. These differences occur even within a single star-forming region. This results in a potentially large range of different disk masses and chemical compositions for systems of similar age and birth environment. While we make preliminary comparisons of molecular fluxes across different star-forming regions, more complete and uniform samples are needed in the future to search for trends with birth environment or age., Comment: Accepted for publication in The Astrophysical Journal

M dwarfs are common host stars to exoplanets but often lack atmospheric abundance measurements. Late-M dwarfs are also good analogs to the youngest substellar companions, which share similar $T_{\rm eff}\sim2300-2800~K$. We present atmospheric analyses for the M7.5 companion HIP 55507 B and its K6V primary star with Keck/KPIC high-resolution ($R\sim35,000$) $K$ band spectroscopy. First, by including KPIC relative radial velocities between the primary and secondary in the orbit fit, we improve the dynamical mass precision by 60% and find $M_B=88.0_{-3.2}^{+3.4}$ $M_{\rm Jup}$, putting HIP 55507 B above the stellar-substellar boundary. We also find that HIP 55507 B orbits its K6V primary star with $a=38^{+4}_{-3}$ AU and $e=0.40\pm0.04$. From atmospheric retrievals of HIP 55507 B, we measure $\rm [C/H]=0.24\pm0.13$, $\rm [O/H]=0.15\pm0.13$, and $\rm C/O=0.67\pm0.04$. Moreover, we strongly detect $\rm ^{13}CO$ ($7.8\sigma$ significance) and tentatively detect $\rm H_2^{18}O$ ($3.7\sigma$ significance) in companion's atmosphere, and measure $\rm ^{12}CO/^{13}CO=98_{-22}^{+28}$ and $\rm H_2^{16}O/H_2^{18}O=240_{-80}^{+145}$ after accounting for systematic errors. From a simplified retrieval analysis of HIP 55507 A, we measure $\rm ^{12}CO/^{13}CO=79_{-16}^{+21}$ and $\rm C^{16}O/C^{18}O=288_{-70}^{+125}$ for the primary star. These results demonstrate that HIP 55507 A and B have consistent $\rm ^{12} C/^{13}C$ and $\rm ^{16}O/^{18}O$ to the $<1\sigma$ level, as expected for a chemically homogeneous binary system. Given the similar flux ratios and separations between HIP 55507 AB and systems with young, substellar companions, our results open the door to systematically measuring $\rm ^{13}CO$ and $\rm H_2^{18}O$ abundances in the atmospheres of substellar or even planetary-mass companions with similar spectral types., Comment: Accepted to ApJ, 28 pages, 14 figures

We present high-resolution $K$-band emission spectra of the quintessential hot Jupiter HD 189733 b from the Keck Planet Imager and Characterizer (KPIC). Using a Bayesian retrieval framework, we fit the dayside pressure-temperature profile, orbital kinematics, mass-mixing ratios of H$_2$O, CO, CH$_4$, NH$_3$, HCN, and H$_2$S, and the $\rm ^{13}CO/^{12}CO$ ratio. We measure mass fractions of $\rm \log H_2O = -2.0^{+0.4}_{-0.4}$ and $\rm \log CO = -2.2^{+0.5}_{-0.5}$, and place upper limits on the remaining species. Notably, we find $\rm \log CH_4 < -4.5$ at 99\% confidence, despite its anticipated presence at the equilibrium temperature of HD 189733 b assuming local thermal equilibrium. We make a tentative ($\sim3\sigma$) detection of $\rm ^{13}CO$, and the retrieved posteriors suggest a $\rm ^{12}C/^{13}C$ ratio similar to or substantially less than the local interstellar value. The possible $\rm ^{13}C$ enrichment would be consistent with accretion of fractionated material in ices or in the protoplanetary disk midplane. The retrieved abundances correspond to a substantially sub-stellar atmospheric $\rm C/O = 0.3\pm0.1$, while the carbon and oxygen abundances are stellar to slightly super-stellar, consistent with core-accretion models which predict an inverse correlation between C/O and metallicity. The specific combination of low C/O and high metallicity suggests significant accretion of solid material may have occurred late in the formation process of HD 189733 b., Comment: 17 pages, 7 figures, 2 tables, accepted in AJ

We present an analysis of the JWST/MIRI-MRS spectrum of Sz114, an accreting M5 star surrounded by a large dust disk with a gap at ~39au. The spectrum is molecular-rich: we report the detection of water, CO, CO2, HCN, C2H2, and H2. The only identified atomic/ionic transition is from [NeII] at 12.81 micron. A distinct feature of this spectrum is the forest of water lines with the 17.22 micron emission surpassing that of most late M-star disks by an order of magnitude in flux and aligning instead with disks of earlier-type stars. Moreover, flux rations of C2H2/H2O and HCN/H2O in Sz114 also resemble those of earlier-type disks, with a slightly elevated CO2/H2O ratio. While accretion heating can boost all infrared lines, the unusual properties of Sz114 could be explained by the young age of the source, its formation under unusual initial conditions (a large massive disk), and/or the presence of dust substructures. The latter delay the inward drift of icy pebbles and thus preserve a lower C/O ratio over an extended period. In contrast, late M-star disks-which are typically faint, small in size, and likely lack significant substructures-may have more quickly depleted the outer icy reservoir and already evolved out of a water-rich inner disk phase. Our findings underscore the unexpected diversity within mid-infrared spectra of late M-star disks, highlighting the need to expand the observational sample for a comprehensive understanding of their variations and thoroughly test pebble drift and planet formation models., Comment: 15 pages, 7 figures, submitted to ApJL

HISPEC is a new, high-resolution near-infrared spectrograph being designed for the W.M. Keck II telescope. By offering single-shot, R=100,000 between 0.98 - 2.5 um, HISPEC will enable spectroscopy of transiting and non-transiting exoplanets in close orbits, direct high-contrast detection and spectroscopy of spatially separated substellar companions, and exoplanet dynamical mass and orbit measurements using precision radial velocity monitoring calibrated with a suite of state-of-the-art absolute and relative wavelength references. MODHIS is the counterpart to HISPEC for the Thirty Meter Telescope and is being developed in parallel with similar scientific goals. In this proceeding, we provide a brief overview of the current design of both instruments, and the requirements for the two spectrographs as guided by the scientific goals for each. We then outline the current science case for HISPEC and MODHIS, with focuses on the science enabled for exoplanet discovery and characterization. We also provide updated sensitivity curves for both instruments, in terms of both signal-to-noise ratio and predicted radial velocity precision., Comment: 25 pages, 9 figures. To appear in the Proceedings of SPIE: Techniques and Instrumentation for Detection of Exoplanets XI, vol. 12680 (2023)

We present Keck/KPIC high-resolution ($R\sim35,000$) $K$-band thermal emission spectroscopy of the ultra-hot Jupiter WASP-33b. The use of KPIC's single-mode fibers greatly improves both blaze and line-spread stabilities relative to slit spectrographs, enhancing the cross-correlation detection strength. We retrieve the dayside emission spectrum with a nested sampling pipeline which fits for orbital parameters, the atmospheric pressure-temperature profile, and molecular abundances.We strongly detect the thermally-inverted dayside and measure mass-mixing ratios for CO ($\log\rm CO_{MMR} = -1.1^{+0.4}_{-0.6}$), H$_2$O ($\log\rm H_2O_{MMR} = -4.1^{+0.7}_{-0.9}$) and OH ($\log\rm OH_{MMR} = -2.1^{+0.5}_{-1.1}$), suggesting near-complete dayside photodissociation of H$_2$O. The retrieved abundances suggest a carbon- and possibly metal-enriched atmosphere, with a gas-phase C/O ratio of $0.8^{+0.1}_{-0.2}$, consistent with the accretion of high-metallicity gas near the CO$_2$ snow line and post-disk migration or with accretion between the soot and H$_2$O snow lines. We also find tentative evidence for $\rm ^{12}CO/^{13}CO \sim 50$, consistent with values expected in protoplanetary disks, as well as tentative evidence for a metal-enriched atmosphere (2--15$\times$ solar). These observations demonstrate KPIC's ability to characterize close-in planets and the utility of KPIC's improved instrumental stability for cross-correlation techniques., Comment: Accepted in AJ, 26 pages, 12 figures

Bulk layered MX2 transition metal chalcogenides (M = Mo, W and X = S, Se) are known to exhibit an indirect to direct band gap transition as the number of layers is reduced. Previous time-resolved work has principally focused on the investigation of the transient evolution of the band structure after photo-excitation, but additional information on the dynamics of the concomitant lattice rearrangement is needed to fully understand this phenomenon. Here, ultrafast electron diffraction is used to probe the atomic motion and bond dilation in monolayer WSe2 with femtosecond temporal resolution. The change in the intensity of the Bragg diffraction spots is characterized by single-exponential dynamics, consistent with a collective response of the lattice during electron-phonon and phonon-phonon equilibration that is repeatable over many hours of illumination with ultrafast pulses. Moreover, a transient and highly anisotropic lattice expansion is observed. A possible explanation for this behavior is axial strain induced by the laser excitation that breaks the degeneracy of the in-plane phonon modes, and that strongly influences the electronic band structure. Such degeneracy-breaking induced by distortions in the lattice are well characterized in static strain measurements, and the results presented here provide valuable insights into the nature and time scales of the structural rearrangement that occurs following optical photo-excitation in monolayer tungsten diselenide., Comment: Submitted to J. Phys. Chem. C, 21 pages, 7 figures

Relating planet formation to atmospheric composition has been a long-standing goal of the planetary science community. So far, most modeling studies have focused on predicting the enrichment of heavy elements and the C/O ratio in giant planet atmospheres. Although this framework provides useful constraints on the potential formation locations of gas giant exoplanets, carbon and oxygen measurements alone are not enough to determine where a given gas giant planet originated. Here, we show that characterizing the abundances of refractory elements (e.g., silicon, iron) can break these degeneracies. Refractory elements are present in the solid phase throughout most of the disk and their atmospheric abundances therefore reflect the solid-to-gas accretion ratio during formation. We introduce a new framework that parameterizes the atmospheric abundances of gas giant exoplanets in the form of three ratios: Si/H, O/Si, and C/Si. Si/H traces the solid-to-gas accretion ratio of a planet and is loosely equivalent to earlier notions of 'metallicity'. For O/Si and C/Si, we present a global picture of their variation with distance and time based on what we know from the solar system meteorites and an updated understanding of the variations of thermal processing within protoplanetary disks. We show that ultra-hot Jupiters are ideal targets for atmospheric characterization studies using this framework, as we can measure the abundances of refractories, oxygen and carbon in the gas phase. Finally, we propose that hot Jupiters with silicate clouds and low water abundances might have accreted their envelopes between the soot line and the water snowline., Comment: accepted to ApJ on Nov 22, 2022. Added DOI and journal ref

Two-dimensional spectroscopic techniques combining terahertz (THz), infrared (IR), and visible pulses offer a wealth of information about coupling among vibrational modes in molecular liquids, thus providing a promising probe of their local structure. However, the capabilities of these spectroscopies are still largely unexplored due to experimental limitations and inherently weak nonlinear signals. Here, through a combination of equilibrium-nonequilibrium molecular dynamics (MD) and a tailored spectrum decomposition scheme, we identify a relationship between the tetrahedral order of liquid water and its two-dimensional IR-IR-Raman (IIR) spectrum. The structure-spectrum relationship can explain the temperature dependence of the spectral features corresponding to the anharmonic coupling between low-frequency intermolecular and high-frequency intramolecular vibrational modes of water. In light of these results, we propose new experiments and discuss the implications for the study of tetrahedrality of liquid water.

The formation and evolution pathway for the directly-imaged multi-planetary system HR 8799 remains mysterious. Accurate constraints on the chemical composition of the planetary atmosphere(s) are key to solving the mystery. We perform a detailed atmospheric retrieval on HR 8799~c to infer the chemical abundances and abundance ratios using a combination of photometric data along with low- and high-resolution spectroscopic data (R$\sim$20-35,000). We specifically retrieve [C/H], [O/H], and C/O and find them to be 0.55$^{+0.36}_{-0.39}$, 0.47$^{+0.31}_{-0.32}$, and 0.67$^{+0.12}_{-0.15}$ at 68\% confidence. The super-stellar C and O abundances, yet a stellar C/O ratio, reveal a potential formation pathway for HR 8799~c. Planet c, and likely the other gas giant planets in the system, formed early on (likely within $\sim$1 Myr), followed by further atmospheric enrichment in C and O through the accretion of solids beyond the CO iceline. The enrichment either preceded or took place during the early phase of the inward migration to the planet current locations., Comment: 19 pages, 6 figures, 3 tables, accepted to AAS journals

We present an analysis of an unusual pattern of water vapor emission from the $\sim$2 Myr-old low-mass binary system VV CrA, as observed in infrared spectra obtained with VLT-CRIRES, VLT-VISIR, and Spitzer-IRS. Each component of the binary shows emission from water vapor in both the L ($\sim3\,\mu$m) and N ($\sim 12\,\mu$m) bands. The N-band and Spitzer spectra are similar to those previously observed from young stars with disks, and are consistent with emission from an extended protoplanetary disk. Conversely, the CRIRES L-band data of VV CrA A show an unusual spectrum, which requires the presence of a water reservoir with high temperature ($T\gtrsim1500$ K), column density ($N_\mathrm{H2O}\sim 3\times10^{20}\ \mathrm{cm}^{-2}$), and turbulent broadening ($v\sim 10$ km s$^{-1}$), but very small emitting area ($A\lesssim0.005$ AU$^2$). Similarity with previously observed water emission from V1331 Cyg (Doppmann et al. 2011) and SVS 13 (Carr et al. 2004) suggests that the presence of such a reservoir may be linked to evolutionary state, perhaps related to the presence of high accretion rates or winds. While the inner disk may harbor such a reservoir, simple Keplerian models do not match well with emitting line shapes, and alternative velocity fields must be considered. We also present a new idea, that the unusual emission could arise in a circumplanetary disk, embedded within the larger VV CrA A protoplanetary disk. Additional data are likely required to determine the true physical origin of this unusual spectral pattern., Comment: 32 pages, 17 figures, 5 appendix figures, 2 tables. Accepted for publication in ApJ

The relative abundances of singly-deuterated methanol isotopologues, [CH$_{2}$DOH]/[CH$_{3}$OD], in star-forming regions deviate from the statistically expected ratio of 3. In Orion KL, the nearest high-mass star-forming region to Earth, the singly-deuterated methanol ratio is about 1, and the cause for this observation has been explored through theory for nearly three decades. We present high-angular resolution observations of Orion KL using the Atacama Large Millimeter/submillimeter Array to map small-scale changes in CH$_{3}$OD column density across the nebula, which provide a new avenue to examine the deuterium chemistry during star and planet formation. By considering how CH$_{3}$OD column densities vary with temperature, we find evidence of chemical processes that can significantly alter the observed column densities. The astronomical data are compared with existing theoretical work and support D-H exchange between CH$_{3}$OH and heavy water (i.e., HDO and D$_{2}$O) at methanol's hydroxyl site in the icy mantles of dust grains. The enhanced CH$_{3}$OD column densities are localized to the Hot Core-SW region, a pattern that may be linked to the coupled evolution of ice mantel chemistry and star formation in giant molecular clouds. This work provides new perspectives on deuterated methanol chemistry in Orion KL and informs considerations that may guide future theoretical, experimental, and observational work., Comment: Accepted for publication in the Journal of Physical Chemistry A

Direct imaging studies have mainly used low-resolution spectroscopy ($R\sim20-100$) to study the atmospheres of giant exoplanets and brown dwarf companions, but the presence of clouds has often led to degeneracies in the retrieved atmospheric abundances (e.g. C/O, metallicity). This precludes clear insights into the formation mechanisms of these companions. The Keck Planet Imager and Characterizer (KPIC) uses adaptive optics and single-mode fibers to transport light into NIRSPEC ($R\sim35,000$ in $K$ band), and aims to address these challenges with high-resolution spectroscopy. Using an atmospheric retrieval framework based on petitRADTRANS, we analyze KPIC high-resolution spectrum ($2.29-2.49~\mu$m) and archival low-resolution spectrum ($1-2.2~\mu$m) of the benchmark brown dwarf HD 4747 B ($m=67.2\pm1.8~M_{\rm{Jup}}$, $a=10.0\pm0.2$ au, $T_{\rm eff}\approx1400$ K). We find that our measured C/O and metallicity for the companion from the KPIC high-resolution spectrum agree with that of its host star within $1-2\sigma$. The retrieved parameters from the $K$ band high-resolution spectrum are also independent of our choice of cloud model. In contrast, the retrieved parameters from the low-resolution spectrum are highly sensitive to our chosen cloud model. Finally, we detect CO, H$_2$O, and CH$_4$ (volume mixing ratio of log(CH$_4$)=$-4.82\pm0.23$) in this L/T transition companion with the KPIC data. The relative molecular abundances allow us to constrain the degree of chemical disequilibrium in the atmosphere of HD 4747 B, and infer a vertical diffusion coefficient that is at the upper limit predicted from mixing length theory., Comment: 33 pages, 16 figures, Accepted to ApJ

NLTT 5306 is a post-common envelope binary made up of a white dwarf host and brown dwarf companion that has shown evidence of inflation and active mass donation despite not filling its Roche lobe. Two proposed mechanisms for the brown dwarf's inflation are magnetic interactions and a high metallicity, cloudy atmosphere. We present moderate resolution ($R\lesssim2000$) $J$ band Keck/NIRSPEC observations of this system. These phase-resolved data allow us to constrain differences between atmospheric parameters of the day- and night-side of the brown dwarf. Our day- and night-side effective temperature measurements are consistent, in agreement with the brightness temperatures measurements from Casewell et al. 2021a. The day-side favors a slightly lower surface gravity, perhaps stemming from the material streaming between the two objects. Finally, our data show a preference for low metallicity models. This would be expected from the system's old age, but provides direct evidence that a high metallicity, cloudy brown dwarf atmosphere is not responsible for the witnessed inflation. These results strengthen the case for magnetic interactions leading to inflation of NLTT 5306 B., Comment: 12 pages, 7 figures, Accepted for publication in AJ

A benchmark brown dwarf (BD) is a BD whose properties (e.g., mass and chemical composition) are precisely and independently measured. Benchmark BDs are valuable in testing theoretical evolutionary tracks, spectral synthesis, and atmospheric retrievals for sub-stellar objects. Here, we report results of atmospheric retrieval on a synthetic spectrum and a benchmark BD -- HR 7672~B -- with \petit. First, we test the retrieval framework on a synthetic PHOENIX BT-Settl spectrum with a solar composition. We show that the retrieved C and O abundances are consistent with solar values, but the retrieved C/O is overestimated by 0.13-0.18, which is $\sim$4 times higher than the formal error bar. Second, we perform retrieval on HR 7672~B using high spectral resolution data (R=35,000) from the Keck Planet Imager and Characterizer (KPIC) and near infrared photometry. We retrieve [C/H], [O/H], and C/O to be $-0.24\pm0.05$, $-0.19\pm0.04$, and $0.52\pm0.02$. These values are consistent with those of HR 7672~A within 1.5-$\sigma$. As such, HR 7672~B is among only a few benchmark BDs (along with Gl 570~D and HD 3651~B) that have been demonstrated to have consistent elemental abundances with their primary stars. Our work provides a practical procedure of testing and performing atmospheric retrieval, and sheds light on potential systematics of future retrievals using high- and low-resolution data., Comment: 29 pages, 17 figures, 5 tables, resubmitted to AAS journals after first revision

Two-dimensional Raman and hybrid terahertz/Raman spectroscopic techniques provide invaluable insight into molecular structure 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., Comment: v2: Added a two-dimensional model system (Fig. 4), updated list of authors, other minor improvements; last 10 pages contain the supplementary material

Gas mass is a fundamental quantity of protoplanetary disks that directly relates to their ability to form planets. Because we are unable to observe the bulk H$_2$ content of disks directly, we rely on indirect tracers to provide quantitative mass estimates. Current estimates for the gas masses of the observed disk population in the Lupus star-forming region are based on measurements of isotopologues of CO. However, without additional constraints, the degeneracy between H$_2$ mass and the elemental composition of the gas leads to large uncertainties in such estimates. Here we explore the gas compositions of seven disks from the Lupus sample representing a range of CO-to-dust ratios. With Band 6 and 7 ALMA observations, we measure line emission for HCO$^+$, HCN, and N$_2$H$^+$. We find a tentative correlation among the line fluxes for these three molecular species across the sample, but no correlation with $^{13}$CO or sub-mm continuum fluxes. For the three disks where N$_2$H$^+$ is detected, we find that a combination of high disk gas masses and sub-interstellar C/H and O/H are needed to reproduce the observed values. We find increases of $\sim$10-100$\times$ previous mass estimates are required to match the observed line fluxes. This study highlights how multi-molecular studies are essential for constraining the physical and chemical properties of the gas in populations of protoplanetary disks and that CO isotopologues alone are not sufficient for determining the mass of many observed disks., Comment: Accepted for publication in The Astrophysical Journal, 19 pages, 15 figures, 2 tables

The Orion Kleinmann-Low nebula (Orion KL) is notoriously complex and exhibits a range of physical and chemical components. We conducted high angular resolution (sub-arcsecond) observations of $^13$CH$_{3}$OH $\nu=0$ ($\sim$0.3$^{\prime\prime}$ and $\sim$0.7$^{\prime\prime}$) and CH$_3$CN $\nu_8=1$ ($\sim$0.2$^{\prime\prime}$ and $\sim$0.9$^{\prime\prime}$) line emission with the Atacama Large Millimeter/submillimeter Array (ALMA) to investigate Orion KL's structure on small spatial scales (${\le}350$ au). Gas kinematics, excitation temperatures, and column densities were derived from the molecular emission via a pixel-by-pixel spectral line fitting of the image cubes, enabling us to examine the small-scale variation of these parameters. Sub-regions of the Hot Core have a higher excitation temperature in a 0.2$^{\prime\prime}$ beam than a 0.9$^{\prime\prime}$ beam, indicative of possible internal sources of heating. Furthermore, the velocity field includes a bipolar ${\sim}7{-}8$ km s$^{-1}$ feature with a southeast-northwest orientation against the surrounding ${\sim}4{-}5$ km s$^{-1}$ velocity field, which may be due to an outflow. We also find evidence of a possible source of internal heating toward the Northwest Clump, since the excitation temperature there is higher in a smaller beam versus a larger beam. Finally, the region southwest of the Hot Core (Hot Core-SW) presents itself as a particularly heterogeneous region bridging the Hot Core and Compact Ridge. Additional studies to identify the (hidden) sources of luminosity and heating within Orion KL are necessary to better understand the nebula and its chemistry., Comment: 28 pages, 15 figures, to be published in ApJ

We reanalyze the multi-epoch direct detections of HD 88133 b and ups And b that were published in Piskorz et al. 2016 and Piskorz et al. 2017, respectively. Using simulations to attempt to reproduce the detections, we find that with the 6 and 7 $L$ band Keck/NIRSPEC epochs analyzed in the original works, the planets would not have been detectable unless they had unreasonably large radii. HD88133 and ups And both have fairly large stellar radii, which contributed to the difficulty in detecting the planets. We take this opportunity to consider how these planets may have been detectable with the small number of epochs originally presented by running simulations both with the upgraded NIRSPEC instrument and with near-zero primary velocities, as recommended by Buzard et al. 2021. While 7 $L$ band NIRSPEC2.0 epochs with near-zero primary velocities would have allowed a strong ($10.8\sigma$) detection of ups And b, many more than 6 $L$ band epochs would have been required for a strong detection of HD88133b, which could be due in part to both this system's large stellar radius and low stellar temperature. This work stresses the importance of careful analytic procedures and the usefulness of simulations in understanding the expected sensitivity of high-resolution spectroscopic data., Comment: 11 pages, 8 figures, Accepted for publication in AJ

Using the Keck Planet Imager and Characterizer (KPIC), we obtained high-resolution (R$\sim$35,000) $K$-band spectra of the four planets orbiting HR 8799. We clearly detected \water{} and CO in the atmospheres of HR 8799 c, d, and e, and tentatively detected a combination of CO and \water{} in b. These are the most challenging directly imaged exoplanets that have been observed at high spectral resolution to date when considering both their angular separations and flux ratios. We developed a forward modeling framework that allows us to jointly fit the spectra of the planets and the diffracted starlight simultaneously in a likelihood-based approach and obtained posterior probabilities on their effective temperatures, surface gravities, radial velocities, and spins. We measured $v\sin(i)$ values of $10.1^{+2.8}_{-2.7}$~km/s for HR 8799 d and $15.0^{+2.3}_{-2.6}$~km/s for HR 8799 e, and placed an upper limit of $< 14$~km/s of HR 8799 c. Under two different assumptions of their obliquities, we found tentative evidence that rotation velocity is anti-correlated with companion mass, which could indicate that magnetic braking with a circumplanetary disk at early times is less efficient at spinning down lower mass planets., Comment: 31 pages, 12 figures, Accepted to AJ

Cross correlation analyses of high resolution spectroscopic data have recently shown great success in directly detecting planetary signals and enabling the characterization of their atmospheres. One such technique aims to observe a system at multiple epochs and combine the measured planetary radial velocities from each epoch into a measurement of the planetary Keplerian orbital velocity $K_p$, constituting a direct detection of the planetary signal. Recent work has shown that in few-epoch ($\sim$5) data sets, unintended structure can arise at a high level, obscuring the planetary detection. In this work, we look to simulations to examine whether there are ways to reduce this structured noise in few-epoch data sets by careful planning of observations. The choice of observation date allows observers to select the primary (stellar) velocity - through a set systemic velocity and chosen barycentric velocity - and the planetary orbital phase, and so we focus on the effects of these two parameters. We find that epochs taken when the primary velocity is near zero, and the stellar lines remain relatively fixed to the telluric rest-frame, greatly reduce the level of structured noise and allow for much stronger planetary detections, on average more than twice the significance of detections made with epochs using randomly selected primary velocities. Following these results, we recommend that observers looking to build up high-resolution multi-epoch data sets target nights when their system has a near-zero primary velocity., Comment: 16 pages, 9 figures, accepted for publication in AJ

Carbon is an essential element for life but its behavior during Earth's accretion is not well understood. Carbonaceous grains in meteoritic and cometary materials suggest that irreversible sublimation, and not condensation, governs carbon acquisition by terrestrial worlds. Through astronomical observations and modeling we show that the sublimation front of carbon carriers in the solar nebula, or the soot line, moved inward quickly so that carbon-rich ingredients would be available for accretion at 1 au after the first million years. On the other hand, geological constraints firmly establish a severe carbon deficit in Earth, requiring the destruction of inherited carbonaceous organics in the majority of its building blocks. The carbon-poor nature of the Earth thus implies carbon loss in its precursor material through sublimation within the first million years., Comment: 21 pages including main article and supplementary materials

Connecting the composition of planet-forming disks with that of gas giant exoplanet atmospheres, in particular through C/O ratios, is one of the key goals of disk chemistry. Small hydrocarbons like $\rm C_2H$ and $\rm C_3H_2$ have been identified as tracers of C/O, as they form abundantly under high C/O conditions. We present resolved $\rm C_3H_2$ observations from the TW Hya Rosetta Stone Project, a program designed to map the chemistry of common molecules at $15-20$ au resolution in the TW Hya disk. Augmented by archival data, these observations comprise the most extensive multi-line set for disks of both ortho and para spin isomers spanning a wide range of energies, $E_u=29-97$ K. We find the ortho-to-para ratio of $\rm C_3H_2$ is consistent with 3 throughout extent of the emission, and the total abundance of both $\rm C_3H_2$ isomers is $(7.5-10)\times10^{-11}$ per H atom, or $1-10$% of the previously published $\rm C_2H$ abundance in the same source. We find $\rm C_3H_2$ comes from a layer near the surface that extends no deeper than $z/r=0.25$. Our observations are consistent with substantial radial variation in gas-phase C/O in TW Hya, with a sharp increase outside $\sim30$ au. Even if we are not directly tracing the midplane, if planets accrete from the surface via, e.g., meridonial flows, then such a change should be imprinted on forming planets. Perhaps interestingly, the HR 8799 planetary system also shows an increasing gradient in its giant planets' atmospheric C/O ratios. While these stars are quite different, hydrocarbon rings in disks are common, and therefore our results are consistent with the young planets of HR 8799 still bearing the imprint of their parent disk's volatile chemistry., Comment: 15 pages, 8 figures, Accepted in ApJ

While high-resolution cross-correlation spectroscopy (HRCCS) techniques have proven effective at characterizing the atmospheres of transiting and non-transiting hot Jupiters, the limitations of these techniques are not well understood. We present a series of simulations of one HRCCS technique, which combines the cross-correlation functions from multiple epochs, to place temperature and contrast limits on the accessible exoplanet population for the first time. We find that planets approximately Saturn-size and larger within $\sim$0.2 AU of a Sun-like star are likely to be detectable with current instrumentation in the $L$-band, a significant expansion compared with the previously-studied population. Cooler ($ \rm T_{eq} \leq 1000$ K) exoplanets are more detectable than suggested by their photometric contrast alone as a result of chemical changes which increase spectroscopic contrast. The $L$-band CH$_4$ spectrum of cooler exoplanets enables robust constraints on the atmospheric C/O ratio at $\rm T_{eq} \sim 900K$, which have proven difficult to obtain for hot Jupiters. These results suggest that the multi-epoch approach to HRCCS can detect and characterize exoplanet atmospheres throughout the inner regions of Sun-like systems with existing high-resolution spectrographs. We find that many epochs of modest signal-to-noise ($\rm S/N_{epoch} \sim 1500$) yield the clearest detections and constraints on C/O, emphasizing the need for high-precision near-infrared telluric correction with short integration times., Comment: 22 pages, 8 figures, accepted to AJ

The thermal structure of protoplanetary disks is a fundamental characteristic of the system that has wide reaching effects on disk evolution and planet formation. In this study, we constrain the 2D thermal structure of the protoplanetary disk TW Hya structure utilizing images of seven CO lines. This includes new ALMA observations of 12CO J=2-1 and C18O J=2-1 as well as archival ALMA observations of 12CO J=3-2, 13CO J=3-2, 6-5, C18O J= 3-2, 6-5. Additionally, we reproduce a Herschel observation of the HD J=1-0 line flux, the spectral energy distribution, and utilize a recent quantification of CO radial depletion in TW Hya. These observations were modeled using the thermochemical code RAC2D, and our best fit model reproduces all spatially resolved CO surface brightness profiles. The resulting thermal profile finds a disk mass of 0.025 Msun and a thin upper layer of gas depleted of small dust with a thickness of approx 1.2% of the corresponding radius. Using our final thermal structure, we find that CO alone is not a viable mass tracer as its abundance is degenerate with the total H2 surface density. Different mass models can readily match the spatially resolved CO line profiles with disparate abundance assumptions. Mass determination requires additional knowledge and, in this work, HD provides the additional constraint to derive the gas mass and supports the inference of CO depletion in the TW Hya disk. Our final thermal structure confirms the use of HD as a powerful probe of protoplanetary disk mass. Additionally, the method laid out in this paper is an employable strategy for extraction of disk temperatures and masses in the future., Comment: 28 pages, 12 main figures, 14 appendix figures. Accepted to ApJ

Formaldehyde (H$_2$CO) is an important precursor to organics like methanol (CH$_3$OH). It is important to understand the conditions that produce H$_2$CO and prebiotic molecules during star and planet formation. H$_2$CO possesses both gas-phase and solid-state formation pathways, involving either UV-produced radical precursors or CO ice and cold ($\lesssim 20$ K) dust grains. To understand which pathway dominates, gaseous H$_2$CO's ortho-to-para ratio (OPR) has been used as a probe, with a value of 3 indicating "warm" conditions and $<3$ linked to cold formation in the solid-state. We present spatially resolved ALMA observations of multiple ortho- and para-H$_2$CO transitions in the TW Hya protoplanetary disk to test H$_2$CO formation theories during planet formation. We find disk-averaged rotational temperatures and column densities of $33\pm2$ K, ($1.1\pm0.1)\times10^{12}$ cm$^{-2}$ and $25\pm2$ K, $(4.4\pm0.3)\times10^{11}$ cm$^{-2}$ for ortho- and para-H$_2$CO, respectively, and an OPR of $2.49\pm0.23$. A radially resolved analysis shows that the observed H$_2$CO emits mostly at rotational temperatures of 30-40 K, corresponding to a layer with $z/R\ge0.25$. The OPR is consistent with 3 within 60 au, the extent of the pebble disk, and decreases beyond 60 au to $2.0\pm0.5$. The latter corresponds to a spin temperature of 12 K, well below the rotational temperature. The combination of relatively uniform emitting conditions, a radial gradient in the OPR, and recent laboratory experiments and theory on OPR ratios after sublimation, lead us to speculate that gas-phase formation is responsible for the observed H$_2$CO across the TW Hya disk.

Molecular D/H ratios are frequently used to probe the chemical past of Solar System volatiles. Yet it is unclear which parts of the Solar Nebula hosted an active deuterium fractionation chemistry. To address this question, we present 0".2-0".4 ALMA observations of DCO+ and DCN 2-1, 3-2 and 4-3 towards the nearby protoplanetary disk around TW Hya, taken as part of the TW Hya Rosetta Stone project, augmented with archival data. DCO+ is characterized by an excitation temperature of ~40 K across the 70 au radius pebble disk, indicative of emission from a warm, elevated molecular layer. Tentatively, DCN is present at even higher temperatures. Both DCO+ and DCN present substantial emission cavities in the inner disk, while in the outer disk the DCO+ and DCN morphologies diverge: most DCN emission originates from a narrow ring peaking around 30~au, with some additional diffuse DCN emission present at larger radii, while DCO+ is present in a broad structured ring that extends past the pebble disk. Based on parametric disk abundance models, these emission patterns can be explained by a near-constant DCN abundance exterior to the cavity, and an increasing DCO+ abundance with radius. There appears to be an active deuterium fractionation chemistry in multiple disk regions around TW Hya, but not in the cold planetesimal-forming midplane and in the inner disk. More observations are needed to explore whether deuterium fractionation is actually absent in these latter regions, and if its absence is a common feature, or something peculiar to the old TW Hya disk., Comment: Accepted for publication in The Astronomical Journal

We demonstrate that halogenated methane 2D-Terahertz Terahertz Raman (2D-TTR) spectra are determined by the complicated structure of the instrument response function (IRF) along $f_1$ and by the molecular coherences along $f_2$. Experimental improvements have helped increase the resolution and dynamic range of the measurements, including accurate THz pulse shape characterization. Sum-frequency excitations convolved with the IRF are found to quantitatively reproduce the 2D-TTR signal. A new Reduced Density Matrix model which incorporates sum-frequency pathways, with linear and harmonic operators fully supports this (re)interpretation of the 2D-TTR spectra., Comment: Supplemental information available after main text

The volatile contents of protoplanetary disks both set the potential for planetary chemistry and provide valuable probes of defining disk system characteristics such as stellar mass, gas mass, ionization, and temperature structure. Current disk molecular inventories are fragmented, however, giving an incomplete picture: unbiased spectral line surveys are needed to assess the volatile content. We present here an overview of such a survey of the protoplanetary disks around the Herbig Ae star MWC 480 and the T Tauri star LkCa 15 in ALMA Band 7, spanning $\sim$36 GHz from 275--317 GHz and representing an order of magnitude increase in sensitivity over previous single-dish surveys. We detect 14 molecular species (including isotopologues), with 5 species (C$^{34}$S, $^{13}$CS, H$_{2}$CS, DNC, and C$_2$D) detected for the first time in protoplanetary disks. Significant differences are observed in the molecular inventories of MWC~480 and LkCa~15, and we discuss how these results may be interpreted in light of the different physical conditions of these two disk systems., Comment: 20 pages, 11 figures

Earth's carbon deficit has been an outstanding problem in our understanding of the formation of our Solar System. A possible solution would be the sublimation of carbon grains at the so-called soot line (~300 K) early in the planet-formation process. Here, we argue that the most likely signatures of this process are an excess of hydrocarbons and nitriles inside the soot line, and a higher excitation temperature for these molecules compared to oxygen-bearing complex organics that desorb around the water snowline (~100 K). Such characteristics have been reported in the literature, for example, in Orion KL, although not uniformly, potentially due to differences in observational settings and analysis methods of different studies or related to the episodic nature of protostellar accretion. If this process is active, this would mean that there is a heretofore unknown component to the carbon chemistry during the protostellar phase that is acting from the top down - starting from the destruction of larger species - instead of from the bottom up from atoms. In the presence of such a top-down component, the origin of organic molecules needs to be re-explored., Comment: Accepted for publication in ApJL. 14 pages, 2 figures, 1 table (4 pages)

The volatile composition of a planet is determined by the inventory of gas and ice in the parent disk. The volatile chemistry in the disk is expected to evolve over time, though this evolution is poorly constrained observationally. We present ALMA observations of C18O, C2H, and the isotopologues H13CN, HC15N, and DCN towards five Class 0/I disk candidates. Combined with a sample of fourteen Class II disks presented in Bergner et al. (2019b), this data set offers a view of volatile chemical evolution over the disk lifetime. Our estimates of C18O abundances are consistent with a rapid depletion of CO in the first ~0.5-1 Myr of the disk lifetime. We do not see evidence that C2H and HCN formation are enhanced by CO depletion, possibly because the gas is already quite under-abundant in CO. Further CO depletion may actually hinder their production by limiting the gas-phase carbon supply. The embedded sources show several chemical differences compared to the Class II stage, which seem to arise from shielding of radiation by the envelope (impacting C2H formation and HC15N fractionation) and sublimation of ices from infalling material (impacting HCN and C18O abundances). Such chemical differences between Class 0/I and Class II sources may affect the volatile composition of planet-forming material at different stages in the disk lifetime., Comment: Accepted to ApJ

We report the 6.5$\sigma$ detection of water from the hot Jupiter HD187123b with a Keplerian orbital velocity $K_p$ of 53 $\pm$ 13 km/s. This high confidence detection is made using a multi-epoch, high resolution, cross correlation technique, and corresponds to a planetary mass of 1.4$^{+0.5}_{-0.3}$ $M_J$ and an orbital inclination of 21 $\pm$ 5$^{\circ}$. The technique works by treating the planet/star system as a spectroscopic binary and obtaining high signal-to-noise, high resolution observations at multiple points across the planet's orbit to constrain the system's binary dynamical motion. All together, seven epochs of Keck/NIRSPEC $L$-band observations were obtained, with five before the instrument upgrade and two after. Using high resolution SCARLET planetary and PHOENIX stellar spectral models, along with a line-by-line telluric absorption model, we were able to drastically increase the confidence of the detection by running simulations that could reproduce, and thus remove, the non-random structured noise in the final likelihood space well. The ability to predict multi-epoch results will be extremely useful for furthering the technique. Here, we use these simulations to compare three different approaches to combining the cross correlations of high resolution spectra and find that the Zucker 2003 log(L) approach is least affected by unwanted planet/star correlation for our HD187123 data set. Furthermore, we find that the same total S/N spread across an orbit in many, lower S/N epochs rather than fewer, higher S/N epochs could provide a more efficient detection. This work provides a necessary validation of multi-epoch simulations which can be used to guide future observations and will be key to studying the atmospheres of further separated, non-transiting exoplanets., Comment: Accepted to AJ, 14 pages, 10 figures

H$_2$CO is one of the most abundant organic molecules in protoplanetary disks and can serve as a precursor to more complex organic chemistry. We present an ALMA survey of H$_2$CO towards 15 disks covering a range of stellar spectral types, stellar ages, and dust continuum morphologies. H$_2$CO is detected towards 13 disks and tentatively detected towards a 14th. We find both centrally-peaked and centrally-depressed emission morphologies, and half of the disks show ring-like structures at or beyond expected CO snowline locations. Together these morphologies suggest that H$_2$CO in disks is commonly produced through both gas-phase and CO-ice-regulated grain-surface chemistry. We extract disk-averaged and azimuthally-averaged H$_2$CO excitation temperatures and column densities for four disks with multiple H$_2$CO line detections. The temperatures are between 20-50K, with the exception of colder temperatures in the DM Tau disk. These temperatures suggest that H$_2$CO emission in disks is generally emerging from the warm molecular layer, with some contributions from the colder midplane. Applying the same H$_2$CO excitation temperatures to all disks in the survey, we find that H$_2$CO column densities span almost three orders of magnitude ($\sim 5 \times 10^{11} - 5 \times 10^{14} \mathrm{cm}^{-2}$). The column densities appear uncorrelated with disk size and stellar age, but Herbig Ae disks may have less H$_2$CO compared to T Tauri disks, possibly because of less CO freeze-out. More H$_2$CO observations towards Herbig Ae disks are needed to confirm this tentative trend, and to better constrain under which disk conditions H$_2$CO and other oxygen-bearing organics efficiently form during planet formation., Comment: 20 pages, 14 figures, 3 figure sets, 9 tables. Published in ApJ (February 2020)

[abridged]CO rovibrational lines are efficient probes of warm molecular gas and can give unique insights into the inner 10 AU of proto-planetary disks. Recent studies have found a relation between the ratio of lines originating from the second and first vibrationally excited state, denoted as $v2/v1$, and the emitting radius of CO. In disks around Herbig Ae stars the vibrational excitation is low when CO lines come from close to the star, and high when lines only probe gas at large radii (more than 5 AU). We aim to find explanations for the observed trends between CO vibrational ratio, emitting radii, and NIR excess, and identify their implications in terms of the physical and chemical structure of inner disks around Herbig stars. Slab models and full disk thermo chemical models are calculated. Simulated observations from the models are directly compared to the data. Broad CO lines with low vibrational ratios are best explained by a warm (400-1300 K) inner disk surface with gas-to-dust ratios below 1000; no CO is detected within/at the inner dust rim, due to dissociation at high temperatures. In contrast, explaining the narrow lines with high vibrational ratios requires an inner cavity of a least 5 AU in both dust and gas, followed by a cool (100-300 K) molecular gas reservoir with gas-to-dust ratios greater than 10000 at the cavity wall. In all cases the CO gas must be close to thermalization with the dust. The high gas-to-dust ratios needed to explain high $v2/v1$ in narrow CO lines for a subset of group I disks can naturally be interpreted as due to the dust traps that have been proposed to explain millimeter dust cavities. The broad lines seen in most group II objects indicate a very flat disk in addition to inner disk substructures within 10 AU that can be related to the substructures recently observed with ALMA., Comment: 17 pages, 16 figures, accepted by A&A

A long standing problem in astrochemistry is the inability of many current models to account for missing sulfur content. Many relatively simple species that may be good candidates to sequester sulfur have not been measured experimentally at the high spectral resolution necessary to enable radioastronomical identification. On the basis of new laboratory data, we report searches for the rotational lines in the microwave, millimeter, and sub-millimeter regions of the sulfur-containing hydrocarbon HCCSH. This simple species would appear to be a promising candidate for detection in space owing to the large dipole moment along its $b$-inertial axis, and because the bimolecular reaction between two highly abundant astronomical fragments (CCH and SH radicals) may be rapid. An inspection of multiple line surveys from the centimeter to the far-infrared toward a range of sources from dark clouds to high-mass star-forming regions, however, resulted in non-detections. An analogous search for the lowest-energy isomer, H$_2$CCS, is presented for comparison, and also resulted in non-detections. Typical upper limits on the abundance of both species relative to hydrogen are $10^{-9}$-$10^{-10}$. We thus conclude that neither isomer is a major reservoir of interstellar sulfur in the range of environments studied. Both species may still be viable candidates for detection in other environments or at higher frequencies, providing laboratory frequencies are available., Comment: Accepted in the Astrophysical Journal

HISPEC (High-resolution Infrared Spectrograph for Exoplanet Characterization) is a proposed diffraction-limited spectrograph for the W.M. Keck Observatory, and a pathfinder for the MODHIS facility project (Multi-Object Diffraction-limited High-resolution Infrared Spectrograph) on the Thirty Meter Telescope. HISPEC/MODHIS builds on diffraction-limited spectrograph designs which rely on adaptively corrected single-mode fiber feeds. Seeing-limited high-resolution spectrographs, by virtue of the conservation of beam etendue, grow in volume following a D^3 power law (D is the telescope diameter), and are subject to daunting challenges associated with their large size. Diffraction-limited spectrographs fed by single mode fibers are decoupled from the telescope input, and are orders of magnitude more compact and have intrinsically stable line spread functions. Their efficiency is directly proportional to the performance of the adaptive optics (AO) system. AO technologies have matured rapidly over the past two decades and are baselined for future extremely large telescopes. HISPEC/MODHIS will take R>100,000 spectra of a few objects in a 10" field-of-view sampled at the diffraction limit (~10-50 mas), simultaneously from 0.95 to 2.4 microns (y-K). The scientific scope ranges from exoplanet infrared precision radial velocities, spectroscopy of transiting, close-in, and directly imaged exoplanets (atmospheric composition and dynamics, RM effect, spin measurements, Doppler imaging), brown dwarf characterization, stellar physics/chemistry, proto-planetary disk kinematics/composition, Solar system, extragalactic science, and cosmology. HISPEC/MODHIS features a compact, cost-effective design optimized to fully exploit the existing Keck-AO and future TMT-NFIRAOS infrastructures and boost the scientific reach of Keck Observatory and TMT soon after first light.