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The transformations of complex metal oxides in aqueous settings must be studied to form a chemical understanding of how technologically relevant nanomaterials impact the environment upon disposal. Owing to the inherent heterogeneity and structural complexity of the ternary intercalation material Li(NixMnyCo1-x-y)O2 (NMC), the mechanisms of chemical processes at the solid–water interface are challenging to model. Here, density functional theory (DFT) + solvent ion methodology is used to study the energetics of stepwise release of two surface metals following unique pathways. The study spans different combinations of metal removal and also considers unique patterns of defects formed by modeling the NMC surface in supercells. The approach here also considers the equilibration of the surface with the surroundings between successive metal removals. A key finding is that a second metal removal prefers to proceed at a metal lattice site adjacent to the initial defect, and this is attributed in part to how the resulting slab with two metal vacancies maintains the most antiferromagnetic couplings between the remaining Ni/Mn. 

Abstract We present the second and final release of optical spectroscopy of Type Ia supernovae (SNe Ia) obtained during the first and second phases of the Carnegie Supernova Project (CSP-I and CSP-II). The newly released data consist of 148 spectra of 30 SNe Ia observed in the course of CSP-I and 234 spectra of 127 SNe Ia obtained during CSP-II. We also present 216 optical spectra of 46 historical SNe Ia, including 53 spectra of 30 SNe Ia observed by the Calán/Tololo Supernova Survey. We combine these observations with previously published CSP data and publicly available spectra to compile a large sample of measurements of spectroscopic parameters at maximum light, consisting of pseudo-equivalent widths and expansion velocities of selected features for 232 CSP and historical SNe Ia (including more than 1000 spectra). Finally, we review some of the strongest correlations between spectroscopic and photometric properties of SNe Ia. Specifically, we define two samples: one consisting of SNe Ia discovered by targeted searches (most of them CSP-I objects) and the other composed of SNe Ia discovered by untargeted searches, which includes most of the CSP-II objects. The analyzed correlations are similar for both samples. We find a larger incidence of SNe Ia belonging to the cool and broad-line Branch subtypes among the events discovered by targeted searches, shallow-silicon SNe Ia are present with similar frequencies in both samples, while core normal SNe Ia are more frequent in untargeted searches. 

Nanoscale complex metal oxides have transformed how technology is used around the world. A ubiquitous example is the class of electroreactive cathodes used in Li-ion batteries, found in portable electronics and electric cars. Lack of recycling infrastructure and financial drivers contribute to improper disposal, and ultimately, introduction of these materials into the environment. Outside of sealed operational conditions, it has been demonstrated that complex metal oxides can transform in the environment, and cause negative biological impact through leaching of cations into aqueous phases. Using a combined DFT and thermodynamics methodology, insights into the mechanism and driving forces of cation release can be studied at the molecular-level. Here, we describe design principles that can be drawn from previous collaborative research on complex metal oxide dissolution of the Li(Ni y Mn z Co 1−y−z )O 2 family of materials, and go on to posit ternary complex metal oxides in the delafossite structure type with controlled release behavior. Using equistoichiometric formulations in the delfossite structure, we use DFT and thermodynamics to model cation release. The release trends are discussed in terms of lattice stability, solution chemistry/solubility limits, and electronic/magnetic properties. Intercalation voltages are calculated and discussed as a predictive metric for potential functionality of the model materials. 

Abstract We present and analyze a near-infrared (NIR) spectrum of the underluminous Type Ia supernova SN 2020qxp/ASASSN-20jq obtained with NIRES at the Keck Observatory, 191 days after B -band maximum. The spectrum is dominated by a number of broad emission features, including the [Fe ii ] at 1.644 μ m, which is highly asymmetric with a tilted top and a peak redshifted by ≈2000 km s −1 . In comparison with 2D non-LTE synthetic spectra computed from 3D simulations of off-center delayed-detonation Chandrasekhar-mass ( M ch ) white dwarf (WD) models, we find good agreement between the observed lines and the synthetic profiles, and are able to unravel the structure of the progenitor’s envelope. We find that the size and tilt of the [Fe ii ] 1.644 μ m profile (in velocity space) is an effective way to determine the location of an off-center delayed-detonation transition (DDT) and the viewing angle, and it requires a WD with a high central density of ∼4 × 10 9 g cm −3 . We also tentatively identify a stable Ni feature around 1.9 μ m characterized by a “pot-belly” profile that is slightly offset with respect to the kinematic center. In the case of SN 2020qxp/ASASSN-20jq, we estimate that the location of the DDT is ∼0.3 M WD off center, which gives rise to an asymmetric distribution of the underlying ejecta. We also demonstrate that low-luminosity and high-density WD SN Ia progenitors exhibit a very strong overlap of Ca and 56 Ni in physical space. This results in the formation of a prevalent [Ca ii ] 0.73 μ m emission feature that is sensitive to asymmetry effects. Our findings are discussed within the context of alternative scenarios, including off-center C/O detonations in He-triggered sub- M Ch WDs and the direct collision of two WDs. Snapshot programs with Gemini/Keck/Very Large Telescope (VLT)/ELT-class instruments and our spectropolarimetry program are complementary to mid-IR spectra by the James Webb Space Telescope (JWST). 

ABSTRACT The observed diversity in Type Ia supernovae (SNe Ia) – the thermonuclear explosions of carbon–oxygen white dwarf stars used as cosmological standard candles – is currently met with a variety of explosion models and progenitor scenarios. To help improve our understanding of whether and how often different models contribute to the occurrence of SNe Ia and their assorted properties, we present a comprehensive analysis of seven nearby SNe Ia. We obtained one to two epochs of optical spectra with Gemini Observatory during the nebular phase (>200 d past peak) for each of these events, all of which had time series of photometry and spectroscopy at early times (the first ∼8 weeks after explosion). We use the combination of early- and late-time observations to assess the predictions of various models for the explosion (e.g. double-detonation, off-centre detonation, stellar collisions), progenitor star (e.g. ejecta mass, metallicity), and binary companion (e.g. another white dwarf or a non-degenerate star). Overall, we find general consistency in our observations with spherically symmetric models for SN Ia explosions, and with scenarios in which the binary companion is another degenerate star. We also present an in-depth analysis of SN 2017fzw, a member of the subgroup of SNe Ia which appear to be transitional between the subluminous ‘91bg-like’ events and normal SNe Ia, and for which nebular-phase spectra are rare. 

Abstract We present 75 near-infrared (NIR; 0.8−2.5 μ m) spectra of 34 stripped-envelope core-collapse supernovae (SESNe) obtained by the Carnegie Supernova Project-II (CSP-II), encompassing optical spectroscopic Types IIb, Ib, Ic, and Ic-BL. The spectra range in phase from pre-maximum to 80 days past maximum. This unique data set constitutes the largest NIR spectroscopic sample of SESNe to date. NIR spectroscopy provides observables with additional information that is not available in the optical. Specifically, the NIR contains the strong lines of He i and allows a more detailed look at whether Type Ic supernovae are completely stripped of their outer He layer. The NIR spectra of SESNe have broad similarities, but closer examination through statistical means reveals a strong dichotomy between NIR “He-rich” and “He-poor” SNe. These NIR subgroups correspond almost perfectly to the optical IIb/Ib and Ic/Ic-BL types, respectively. The largest difference between the two groups is observed in the 2 μ m region, near the He i λ 2.0581 μ m line. The division between the two groups is not an arbitrary one along a continuous sequence. Early spectra of He-rich SESNe show much stronger He i λ 2.0581 μ m absorption compared to the He-poor group, but with a wide range of profile shapes. The same line also provides evidence for trace amounts of He in half of our SNe in the He-poor group.