Heteroleptic samarium(III) halide complexes probed by fluorescence-detected L3-edge X-ray absorption spectroscopy

Addition of various oxidants to the near-linear Sm(II) complex [Sm(N††)2] (1), where N†† is the bulky bis(triisopropylsilyl)amide ligand {N(SiiPr3)2}, afforded a family of heteroleptic three-coordinate Sm(III) halide complexes, [Sm(N††)2(X)] (X = F, 2-F; Cl, 2-Cl; Br, 2-Br; I, 2-I). In addition, the trinuclear cluster [{Sm(N††)}3(μ2-I)3(μ3-I)2] (3), which formally contains one Sm(II) and two Sm(III) centres, was isolated during the synthesis of 2-I. Complexes 2-X are remarkably stable towards ligand redistribution, which is often a facile process for heteroleptic complexes of smaller monodentate ligands in lanthanide chemistry, including the related bis(trimethylsilyl)amide {N(SiMe3)2} (N′′). Complexes 2-X and 3 have been characterised by single crystal X-ray diffraction, elemental analysis, multinuclear NMR, FTIR and electronic spectroscopy. The Lα1 fluorescence-detected X-ray absorption spectrum recorded at the Sm L3-edge for 2-X exhibited a resolved pre-edge peak defined as an envelope quadrupole-allowed 2p → 4f transition. The X-ray absorption spectral features were successfully reproduced using time-dependent density functional theoretical (TD-DFT) calculations that synergistically supports the experimental observations as well as the theoretical model upon which the electronic structure and bonding in lanthanide complexes is derived

A modeling case for high atmospheric oxygen concentrations during the Mesozoic and Cenozoic

Changes in atmospheric oxygen concentration over Earth history are commonly related to the evolution of animals and plants. But there is no direct geochemical proxy for O2 levels, meaning that estimations rely heavily on modeling approaches. The results of such studies differ greatly, to the extent that today's atmospheric mixing ratio of 21% might be either the highest or lowest level during the past 200 m.y. Long-term oxygen sources, such as the burial in sediments of reduced carbon and sulfur species, are calculated in models by representation of nutrient cycling and estimation of productivity, or by isotope mass balance (IMB)—a technique in which burial rates are inferred in order to match known isotope records. Studies utilizing these different techniques produce conflicting estimates for paleoatmospheric O2, with nutrient-weathering models estimating concentrations close to, or above, that of the present day, and IMB models estimating low O2, especially during the Mesozoic. Here we re-assess the IMB technique using the COPSE biogeochemical model. IMB modelling is confirmed to be highly sensitive to assumed carbonate δ13C, and when this input is defined following recent compilations, predicted O2 is significantly higher and in reasonable agreement with that of non-IMB techniques. We conclude that there is no model-based support for low atmospheric oxygen concentrations during the past 200 m.y. High Mesozoic O2 is consistent with wildfire records and the development of plant fire adaptions, but links between O2 and mammal evolution appear more tenuous

Effects of Disturbance and Conspecific Negative Density Dependence on Forest Composition and Diversity: A Simulation-Based Approach

Forests provide a wide range of services to humans and create critical habitat for countless species. Tree species composition and diversity, key attributes of forest health and identity, are influenced by both disturbance and conspecific negative density dependence (CNDD). These factors have been thoroughly researched in isolation, but much less is known about how they interact. We present results of a simulation model constructed to investigate the interactions of variable CNDD strengths and disturbance types. We found that while CNDD consistently increased diversity, the magnitude of this effect was heavily influenced by the disturbance regime. The difference between weak and strong CNDD was most pronounced with understory disturbance, and the greatest diversity overall was achieved when strong CNDD was paired with understory disturbance. Empirical studies of CNDD have yielded widely divergent results. Our study suggests a comprehensive understanding of forest ecosystems may require simultaneous consideration of both disturbance and CNDD

Long-Period Giant Companions to Three Compact, Multiplanet Systems

Understanding the relationship between long-period giant planets and multiple smaller short-period planets is critical for formulating a complete picture of planet formation. This work characterizes three such systems. We present Kepler-65, a system with an eccentric (e = 0.28 ± 0.07) giant planet companion discovered via radial velocities (RVs) exterior to a compact, multiply transiting system of sub-Neptune planets. We also use precision RVs to improve mass and radius constraints on two other systems with similar architectures, Kepler-25 and Kepler-68. In Kepler-68 we propose a second exterior giant planet candidate. Finally, we consider the implications of these systems for planet formation models, particularly that the moderate eccentricity in Kepler-65\u27s exterior giant planet did not disrupt its inner system

CKS VIII: Eccentricities of Kepler Planets and Tentative Evidence of a High Metallicity Preference for Small Eccentric Planets

Characterizing the dependence of the orbital architectures and formation environments on the eccentricity distribution of planets is vital for understanding planet formation. In this work, we perform statistical eccentricity studies of transiting exoplanets using transit durations measured via Kepler combined with precise and accurate stellar radii from the California-Kepler Survey and Gaia. Compared to previous works that characterized the eccentricity distribution from transit durations, our analysis benefits from both high precision stellar radii ($\sim$3%) and a large sample of $\sim$1000 planets. We observe that that systems with only a single observed transiting planet have a higher mean eccentricity ($\bar{e} \sim 0.21$) than systems with multiple transiting planets ($\bar{e} \sim 0.05$), in agreement with previous studies. We confirm the preference for high and low eccentricity subpopulations among the singly transiting systems. Finally, we show suggestive new evidence that high $e$ planets in the Kepler sample are preferentially found around high metallicity ([Fe/H] $>0$) stars. We conclude by discussing the implications on planetary formation theories

The Discovery of the Long-Period, Eccentric Planet Kepler-88 d and System Characterization with Radial Velocities and Photodynamical Analysis

We present the discovery of Kepler-88 d (P_d = 1403±14 , M sin i_d = 970±50M⊕ = 3.05±0.16M_J, e_d = 0.42±0.04) based on six years of radial velocity (RV) follow-up from the W. M. Keck Observatory High Resolution Echelle Spectrometer spectrograph. Kepler-88 has two previously identified planets. Kepler-88 b (KOI-142.01) transits in the NASA Kepler photometry and has very large transit timing variations (TTVs). Nesvorný et al. performed a dynamical analysis of the TTVs to uniquely identify the orbital period and mass of the perturbing planet (Kepler-88 c), which was later was confirmed with RVs from the Observatoire de Haute-Provence (OHP). To fully explore the architecture of this system, we performed photodynamical modeling on the Kepler photometry combined with the RVs from Keck and OHP and stellar parameters from spectroscopy and Gaia. Planet d is not detectable in the photometry, and long-baseline RVs are needed to ascertain its presence. A photodynamical model simultaneously optimized to fit the RVs and Kepler photometry yields the most precise planet masses and orbital properties yet for b and c: P_b = 10.91647±0.00014days, M_b = 9.5±1.2M⊕, P_c = 22.2649±0.0007 days, and M_c = 214.1±5.3M⊕. The photodynamical solution also finds that planets b and c have low eccentricites and low mutual inclination, are apsidally anti-aligned, and have conjunctions on the same hemisphere of the star. Continued RV follow-up of systems with small planets will improve our understanding of the link between inner planetary system architectures and giant planets

Schizophrenia and cardiometabolic abnormalities:A Mendelian randomization study

Background: Individuals with a diagnosis of schizophrenia are known to be at high risk of premature mortality due to poor physical health, especially cardiovascular disease, diabetes, and obesity. The reasons for these physical health outcomes within this patient population are complex. Despite well-documented cardiometabolic adverse effects of certain antipsychotic drugs and lifestyle factors, schizophrenia may have an independent effect. Aims: To investigate if there is evidence that schizophrenia is causally related to cardiometabolic traits (blood lipids, anthropometric traits, glycaemic traits, blood pressure) and vice versa using bi-directional two-sample Mendelian randomization (MR) analysis. Methods: We used 185 genetic variants associated with schizophrenia from the latest Psychiatric Genomics Consortium GWAS (n = 130,644) in the forward analysis (schizophrenia to cardiometabolic traits) and genetic variants associated with the cardiometabolic traits from various consortia in the reverse analysis (cardiometabolic traits to schizophrenia), both at genome-wide significance (5 × 10−8). The primary method was inverse-variance weighted MR, supported by supplementary methods such as MR-Egger, as well as median and mode-based methods. Results: In the forward analysis, schizophrenia was associated with slightly higher low-density lipoprotein (LDL) cholesterol levels (0.013 SD change in LDL per log odds increase in schizophrenia risk, 95% CI, 0.001–0.024 SD; p = 0.027) and total cholesterol levels (0.013 SD change in total cholesterol per log odds increase in schizophrenia risk, 95% CI, 0.002–0.025 SD; p = 0.023). However, these associations did not survive multiple testing corrections. There was no evidence of a causal effect of cardiometabolic traits on schizophrenia in the reverse analysis. Discussion: Dyslipidemia and obesity in schizophrenia patients are unlikely to be driven primarily by schizophrenia itself. Therefore, lifestyle, diet, antipsychotic drugs side effects, as well as shared mechanisms for metabolic dysfunction and schizophrenia such as low-grade systemic inflammation could be possible reasons for the apparent increased risk of metabolic disease in people with schizophrenia. Further research is needed to examine the shared immune mechanism hypothesis.</p

Dynamics and Formation of the Near-Resonant K2-24 System: Insights from Transit-Timing Variations and Radial Velocities

While planets between the size of Uranus and Saturn are absent within the Solar System, the star K2-24 hosts two such planets, K2-24b and c, with radii equal to $5.4~R_E$ and $7.5~R_E$, respectively. The two planets have orbital periods of 20.9 days and 42.4 days, residing only 1% outside the nominal 2:1 mean-motion resonance. In this work, we present results from a coordinated observing campaign to measure planet masses and eccentricities that combines radial velocity (RV) measurements from Keck/HIRES and transit-timing measurements from K2 and Spitzer. K2-24b and c have low, but non-zero, eccentricities of $e_1 \sim e_2 \sim 0.08$. The low observed eccentricities provide clues regarding the formation and dynamical evolution of K2-24b and K2-24c, suggesting that they could be the result of stochastic gravitational interactions with a turbulent protoplanetary disk, among other mechanisms. K2-24b and c are $19\pm2~M_E$ and $15\pm2~M_E$, respectively; K2-24c is 20% less massive than K2-24b, despite being 40% larger. Their large sizes and low masses imply large envelope fractions, which we estimate at $26^{+3}_{-3}\%$ and $52^{+5}_{-3}\%$. In particular, K2-24c's large envelope presents an intriguing challenge to the standard model of core nucleated accretion that predicts the onset of runaway accretion when $f_{env} \approx 50\%$.Comment: 14 pages, 9 figures, 2 tables, accepted to A