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Supported metal nanoparticle (NP) catalysts are vital for the sustainable production of chemicals, but their design and implementation are limited by the ability to identify and characterize their structures and atomic sites that are correlated with high catalytic activity. Identification of these ''active sites'' has relied heavily on extrapolation to supported NP systems from investigation of idealized surfaces, experimentally using single crystals or supported NPs which are always modelled computationally using slab or regular polyhedra models. However, the ability of these methods to predict catalytic activity remains qualitative at best, as the structure of metal NPs in reactive environments has only been speculated from indirect experimental observations, or otherwise remains wholly unknown. Here, by circumventing these limitations for highly accurate simulation methods, we provide direct atomistic insight into the dynamic restructuring of metal NPs by combining in situ spectroscopy with molecular dynamics simulations powered by a machine learned force field. We find that in reactive environments, NP surfaces evolve to a state with poorly defined atomic order, while the core of the NP may remain bulk-like. These insights prove that long-standing conceptual models based on idealized faceting for small metal NP systems are not representative of real systems under exposure to reactive environments. We show that the resultant structure can be elucidated by combining advanced spectroscopy and computational tools. This discovery exemplifies that to enable faithful quantitative predictions of catalyst function and stability, we must move beyond idealized-facet experimental and theoretical models and instead employ systems which include realistic surface structures that respond to relevant physical and chemical conditions., Comment: 18 pages, 11 figures (4 main, 7 SI)

Multi-component metal nanoparticles (NPs) are of paramount importance in the chemical industry, as most processes therein employ heterogeneous catalysts. While these multi-component systems have been shown to result in higher product yields, improved selectivities, and greater stability through catalytic cycling, the structural dynamics of these materials in response to various stimuli (e.g. temperature, adsorbates, etc.) are not understood with atomistic resolution. Here, we present a highly accurate equivariant machine-learned force field (MLFF), constructed from ab initio training data collected using Bayesian active learning, that is able to reliably simulate PdAu surfaces and NPs in response to thermal treatment as well as exposure to reactive H$_2$ atmospheres. We thus provide a single model that is able to reliably describe the full space of geometric and chemical complexity for such a heterogeneous catalytic system across single crystals, gas-phase interactions, and NPs reacting with H$_2$, including catalyst degradation and explicit reactivity. Ultimately, we provide direct atomistic evidence that verifies existing experimental hypotheses for bimetallic catalyst deactivation under reaction conditions, namely that Pd preferentially segregates into the Au bulk through aggressive catalytic cycling and that this degradation is site-selective, as well as the reactivity for hydrogen exchange as a function of Pd ensemble size. We demonstrate that understanding of the atomistic evolution of these active sites is of the utmost importance, as it allows for design and control of material structure and corresponding performance, which can be vetted in silico., Comment: 19 pages, 8 figures (main + SI)

Since 2015, the Emerging Researchers in Exoplanetary Science (ERES) conference has provided a venue for early-career researchers in exoplanetary astronomy, astrophysics, and planetary science to share their research, network, and build new collaborations. ERES stands out in that it is spearheaded by early-career researchers, providing a unique attendance experience for the participants and a professional experience for the organizers. In this Bulletin, we share experiences and lessons learned from the perspective of the organizing committee for the 2023 edition of ERES. For this eighth ERES conference, we hosted over 100 participants in New Haven, CT, for a three-day program. This manuscript is aimed primarily toward groups of early-career scientists who are planning a conference for their fields of study. We anticipate that this Bulletin will continue dialogue within the academic community about best practices for equitable event organization., Comment: To appear in the Bulletin of the American Astronomical Society (see DOI); 13 pages, 6 figures

A large fraction of white dwarfs (WDs) have metal-polluted atmospheres, which are produced by accreting material from remnant planetary systems. The composition of the accreted debris broadly resembles that of rocky Solar System objects. Volatile-enriched debris with compositions similar to long-period comets (LPCs) is rarely observed. We attempt to reconcile this dearth of volatiles with the premise that exo-Oort clouds (XOCs) occur around a large fraction of planet-hosting stars. We estimate the comet accretion rate from an XOC analytically, adapting the 'loss cone' theory of LPC delivery in the Solar System. We investigate the dynamical evolution of an XOC during late stellar evolution. Using numerical simulations, we show that 1 to 30 per cent of XOC objects remain bound after anisotropic stellar mass loss imparting a WD natal kick of $\sim$1 km/s. We also characterize the surviving comets' distribution function. Surviving planets orbiting a WD can prevent the accretion of XOC comets by the star. A planet's 'dynamical barrier' is effective at preventing comet accretion if the energy kick imparted by the planet exceeds the comet's orbital binding energy. By modifying the loss cone theory, we calculate the amount by which a planet reduces the WD's accretion rate. We suggest that the scarcity of volatile-enriched debris in polluted WDs is caused by an unseen population of 10-100 AU scale giant planets acting as barriers to incoming LPCs. Finally, we constrain the amount of volatiles delivered to a planet in the habitable zone of an old, cool WD., Comment: 18 pages, 12 figures; submitted to MNRAS. Comments welcome!

We introduce a formalism to efficiently calculate lasing modes and optical power flow in multi-section lasers with open boundaries. The formalism is underpinned by a projection of the complex-valued electric field and its spatial derivative onto a suitably extended complex $\mathcal{Z}$-plane, to reduce the order of the problem and simplify analysis. In a single-section laser, we show that a laser mode is a loxodrome on the extended complex $\mathcal{Z}$-plane. In a multi-section laser, we obtain loxodromes for individual sections of the laser. Then, a multi-section mode is constructed by continuously concatenating individual loxodromes from each section using the open boundary conditions. A natural visualization of this construction is given by stereographic projection of the extended complex $\mathcal{Z}$-plane onto the Riemann sphere. Our formalism simplifies analysis of lasing modes in open multi-section lasers and provides new insight into the mode geometry and degeneracy.

About ten percent of Sun-like ($1$-$2 M_\odot$) stars will engulf a $1$-$10 M_{\rm J}$ planet as they expand during the red giant branch (RGB) or asymptotic giant branch (AGB) phase of their evolution. Once engulfed, these planets experience a strong drag force in the star's convective envelope and spiral inward, depositing energy and angular momentum. For these mass ratios, the inspiral takes $\sim 10$-$10^{2}$ years ($\sim 10^{2}$-$10^{3}$ orbits); the planet undergoes tidal disruption at a radius of $\sim R_\odot$. We use the Modules for Experiments in Stellar Astrophysics (MESA) software instrument to track the stellar response to the energy deposition while simultaneously evolving the planetary orbit. For RGB stars, as well as AGB stars with $M_{\rm p} \lesssim 5 M_{\rm J}$ planets, the star responds quasistatically but still brightens measurably on a timescale of years. In addition, asteroseismic indicators, such as the frequency spacing or rotational splitting, differ before and after engulfment. For AGB stars, engulfment of a $M_{\rm p} \gtrsim 5 M_{\rm J}$ planet drives supersonic expansion of the envelope, causing a bright, red, dusty eruption similar to a "luminous red nova." Based on the peak luminosity, color, duration, and expected rate of these events, we suggest that engulfment events on the AGB could be a significant fraction of low-luminosity red novae in the Galaxy. We do not find conditions where the envelope is ejected prior to the planet's tidal disruption, complicating the interpretation of short-period giant planets orbiting white dwarfs as survivors of common-envelope evolution., Comment: 24 pages, 11 figures, 1 table. Accepted to ApJ

Secular oscillations in multi-planet systems can drive chaotic evolution of a small inner body through non-linear resonant perturbations. This "secular chaos" readily pushes the inner body to an extreme eccentricity, triggering tidal interactions or collision with the central star. We present a numerical study of secular chaos in systems with two planets and test particles using the ring-averaging method, with emphasis on the relationship between the planets' properties and the time-scale and efficiency of chaotic diffusion. We find that secular chaos can excite extreme eccentricities on time-scales spanning several orders of magnitude in a given system. We apply our results to the evolution of planetary systems around white dwarfs (WDs), specifically the tidal disruption and high-eccentricity migration of planetesimals and planets. We find that secular chaos in a planetesimal belt driven by large ($\gtrsim 10 M_{\oplus}$), distant ($\gtrsim 10 \, {\rm au}$) planets can sustain metal accretion onto a WD over Gyr time-scales. We constrain the total mass of planetesimals initially present within the chaotic zone by requiring that the predicted mass delivery rate to the Roche limit be consistent with the observed metal accretion rates of WDs with atmospheric pollution throughout the cooling sequence. Based on the occurrence of long-period exoplanets and exo-asteroid belts, we conclude that secular chaos can be a significant (perhaps dominant) channel for polluting solitary WDs. Secular chaos can also produce short-period planets and planetesimals around WDs in concert with various circularization mechanisms. We discuss prospects for detecting exoplanets driving secular chaos around WDs using direct imaging and microlensing., Comment: 21 pages, 10 figures, 2 tables; accepted in MNRAS

WD 1856+534 b is a Jupiter-sized, cool giant planet candidate transiting the white dwarf WD 1856+534. Here, we report an optical transmission spectrum of WD 1856+534 b obtained from ten transits using the Gemini Multi-Object Spectrograph. This system is challenging to observe due to the faintness of the host star and the short transit duration. Nevertheless, our phase-folded white light curve reached a precision of 0.12 %. WD 1856+534 b provides a unique transit configuration compared to other known exoplanets: the planet is $8\times$ larger than its star and occults over half of the stellar disc during mid-transit. Consequently, many standard modeling assumptions do not hold. We introduce the concept of a `limb darkening corrected, time-averaged transmission spectrum' and propose that this is more suitable than $(R_{\mathrm{p}, \lambda} / R_{\mathrm{s}})^2$ for comparisons to atmospheric models for planets with grazing transits. We also present a modified radiative transfer prescription. Though the transmission spectrum shows no prominent absorption features, it is sufficiently precise to constrain the mass of WD 1856+534 b to be > 0.84 M$_\mathrm{J}$ (to $2 \, \sigma$ confidence), assuming a clear atmosphere and a Jovian composition. High-altitude cloud decks can allow lower masses. WD 1856+534 b could have formed either as a result of common envelope evolution or migration under the Kozai-Lidov mechanism. Further studies of WD 1856+534 b, alongside new dedicated searches for substellar objects around white dwarfs, will shed further light on the mysteries of post-main sequence planetary systems., Comment: 21 pages, 10 figures, accepted for publication in AJ

We investigate the possible origin of the transiting giant planet WD1856+534b, the first strong exoplanet candidate orbiting a white dwarf, through high-eccentricity migration (HEM) driven by the Lidov-Kozai (LK) effect. The host system's overall architecture is an hierarchical quadruple in the '2+2' configuration, owing to the presence of a tertiary companion system of two M-dwarfs. We show that a secular inclination resonance in 2+2 systems can significantly broaden the LK window for extreme eccentricity excitation ($e \gtrsim 0.999$), allowing the giant planet to migrate for a wide range of initial orbital inclinations. Octupole effects can also contribute to the broadening of this 'extreme' LK window. By requiring that perturbations from the companion stars be able to overcome short-range forces and excite the planet's eccentricity to $e \simeq 1$, we obtain an absolute limit of $a_{1} \gtrsim 8 \, {\rm AU} \, (a_{3} / 1500 \, {\rm AU})^{6/7}$ for the planet's semi-major axis just before migration (where $a_{3}$ is the semi-major axis of the 'outer' orbit). We suggest that, to achieve a wide LK window through the 2+2 resonance, WD1856b likely migrated from $30 \, {\rm AU} \lesssim a_{1} \lesssim 60 \, {\rm AU}$, corresponding to $\sim 10$--$20 \, {\rm AU}$ during the host's main-sequence phase. We discuss possible difficulties of all flavours of HEM affecting the occurrence rate of short-period giant planets around white dwarfs., Comment: 8 pages, 4 figures, 1 table; MNRAS 501 (2021) 507-514

Several white dwarfs with atmospheric metal pollution have been found to host small planetary bodies (planetesimals) orbiting near the tidal disruption radius. We study the physical properties and dynamical origin of these bodies under the hypothesis that they underwent high-eccentricity migration from initial distances of several astronomical units. We examine two plausible mechanisms for orbital migration and circularization: tidal friction and ram-pressure drag in a compact disc. For each mechanism, we derive general analytic expressions for the evolution of the orbit that can be rescaled for various situations. We identify the physical parameters that determine whether a planetesimal's orbit can circularize within the appropriate time-scale and constrain these parameters based on the properties of the observed systems. For tidal migration to work, an internal viscosity similar to that of molten rock is required, and this may be naturally produced by tidal heating. For disc migration to operate, a minimal column density of the disc is implied; the inferred total disc mass is consistent with estimates of the total mass of metals accreted by polluted WDs., Comment: 17 pages, 13 figures, 2 appendices

Predicting the outcome of a chemical reaction using efficient computational models can be used to develop high-throughput screening techniques. This can significantly reduce the number of experiments needed to be performed in a huge search space, which saves time, effort and expense. Recently, machine learning methods have been bolstering conventional structure-activity relationships used to advance understanding of chemical reactions. We have developed a model to predict the products of catalytic reactions on the surface of oxygen-covered and bare gold using machine learning. Using experimental data, we developed a machine learning model that maps reactants to products, using a chemical space representation. This involves predicting a chemical space value for the products, and then matching this value to a molecular structure chosen from a database. The database was developed by applying a set of possible reaction outcomes using known reaction mechanisms. Our machine learning approach complements chemical intuition in predicting the outcome of several types of chemical reactions. In some cases, machine learning makes correct predictions where chemical intuition fails. We achieve up to 93% prediction accuracy for a small data set of less than two hundred reactions.

We investigate the constraints on the formation of, and tidal dissipation processes in, hot Jupiters (HJs) that can be inferred based on reliable knowledge of the age of a system or population. Particular attention is paid to the role of young systems (such as those in open clusters or star-forming regions) in such studies. For an ensemble of coeval HJ (or proto-HJ) systems, we quantify the effect of age on the distribution of orbital eccentricities with respect to orbital periods as well as the location of the observed "pile-up" feature. We expect the effects of pre-main-sequence stellar evolution to be important only if a substantial fraction of HJs approach their current orbits early in protostellar contraction (ages less than 10 Myr). Application to the HJs presently known in the cluster M67 yields constraints on the dissipation roughly consistent with those gleaned from planets in the field; for those in the Hyades and Praesepe, our results suggest a higher degree of dissipation at early times than that inferred from other populations., Comment: 14 pages, 9 figures. Submitted to MNRAS on 2017 November 27