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At least 199 records · Page 11

SDSS-IV MaNGA: Stellar M/L gradients and the M/L-colour relation in galaxies

The stellar mass-to-light ratio gradient in SDSS r-band ∇(M * /L r ) of a galaxy depends on its mass assembly history, which is imprinted in its morphology and gradients of age, metallicity, and stellar initial mass function (IMF). Taking a MaNGA sample of 2051 galaxies with stellar masses ranging from 10 9 to 10 12 M ⊙ released in SDSS DR15, we focus on face-on galaxies, without merger and bar signatures, and investigate the dependence of the 2D ∇(M * /L r ) on other galaxy properties, including M * /L r -colour relationships by assuming a fixed Salpeter IMF as the mass normalization reference. The median gradient is ∇M * /L r ~ –0.1 (i.e. the M * /L r is larger at the centre) for massive galaxies, becomes flat around M * ~ 10 10 M ⊙ and change sign to ∇M * /L r ~ 0.1 at the lowest masses. The M * /L r inside a half-light radius increases with increasing galaxy stellar mass; in each mass bin, early-type galaxies have the highest value, while pure-disc late-type galaxies have the smallest. Correlation analyses suggest that the mass-weighted stellar age is the dominant parameter influencing the M * /L r profile, since a luminosity-weighted age is easily affected by star formation when the specific star formation rate (sSFR) inside the half-light radius is higher than 10 –3 Gyr –1 . With increased sSFR gradient, one can obtain a steeper negative ∇(M * /L r ). The scatter in the slopes of M * /L-colour relations increases with increasing sSFR, for example, the slope for post-starburst galaxies can be flattened to 0.45 from the global value 0.87 in the M * /L versus g – r diagram. Hence converting galaxy colours to M * /L should be done carefully, especially for those galaxies with young luminosity-weighted stellar ages, which can have quite different star formation histories.

79 ASTRONOMY AND ASTROPHYSICS↗

What drives the scatter of local star-forming galaxies in the BPT diagrams? A Machine Learning based analysis

ABSTRACT We investigate which physical properties are most predictive of the position of local star forming galaxies on the BPT diagrams, by means of different Machine Learning (ML) algorithms. Exploiting the large statistics from the Sloan Digital Sky Survey (SDSS), we define a framework in which the deviation of star-forming galaxies from their median sequence can be described in terms of the relative variations in a variety of observational parameters. We train artificial neural networks (ANN) and random forest (RF) trees to predict whether galaxies are offset above or below the sequence (via classification), and to estimate the exact magnitude of the offset itself (via regression). We find, with high significance, that parameters primarily associated to variations in the nitrogen-over-oxygen abundance ratio (N/O) are the most predictive for the [N ii]-BPT diagram, whereas properties related to star formation (like variations in SFR or EW(H α)) perform better in the [S ii]-BPT diagram. We interpret the former as a reflection of the N/O–O/H relationship for local galaxies, while the latter as primarily tracing the variation in the effective size of the S+ emitting region, which directly impacts the [S ii] emission lines. This analysis paves the way to assess to what extent the physics shaping local BPT diagrams is also responsible for the offsets seen in high redshift galaxies or, instead, whether a different framework or even different mechanisms need to be invoked.

79 ASTRONOMY AND ASTROPHYSICS↗

RRab variables with identical light-curve shapes at different pulsation periods

In this paper, we report on the detection of RRab stars with quasi-identical-shape light curves but period differences as large as 0.05–0.21 d using the Galactic bulge data of the OGLE-IV survey. We have examined stars with shorter periods than the Oosterhoff I ridge of the bulge. These stars generally have smaller amplitudes and larger Fourier phase-differences than the typical bulge RRab stars have at the same period. Many of these ‘anomalous’ stars have good-quality light curves without any sign of the Blazhko modulation. Examining their Fourier parameters revealed that several of these stars show very similar light curve to the typical bulge RR Lyrae. We found hundreds of quasi-identical-shape light-curve pairs with different periods between the ‘anomalous’- and the ‘normal’-position RRab stars based on the OGLE I-band data. The OGLE V-band, and the archive VVV and MACHO surveys K s -, b- and r -band data of these stars were also checked for light-curve-shape similarity. Finally, 149 pairs with identical-shape light curves in each available photometric band were identified. Calculating the physical properties of the variables using empirical formulae, on average, −0.5 dex, −0.13 mag, 0.67, and 165 K differences between the [Fe/H], M V , R/R ⊙ , and T eff values of the members of the pairs are derived, being the short-period stars less metal-poor, fainter, smaller, and hotter than the long-period variables. To explain the existence of variables with different physical properties and pulsation periods but with identical-shape light curves is a challenging task for modelling.

79 ASTRONOMY AND ASTROPHYSICS↗

Modeling the Enceladus dust plume based on in situ measurements performed with the Cassini Cosmic Dust Analyzer

We analyzed data recorded by the Cosmic Dust Analyzer on board the Cassini spacecraft during Enceladus dust plume traversals. Our focus was on profiles of relative abundances of grains of different compositional types derived from mass spectra recorded with the Dust Analyzer subsystem during the Cassini flybys E5 and E17. The E5 profile, corresponding to a steep and fast traversal of the plume, has already been analyzed. In this paper, we included a second profile from the E17 flyby involving a nearly horizontal traversal of the south polar terrain at a significantly lower velocity. Additionally, we incorporated dust detection rates from the High Rate Detector subsystem during flybys E7 and E21. We derived grain size ranges in the different observational data sets and used these data to constrain parameters for a new dust plume model. This model was constructed using a mathematical description of dust ejection implemented in the software package DUDI. Further constraints included published velocities of gas ejection, positions of gas and dust jets, and the mass production rate of the plume. Our model employs two different types of sources: diffuse sources of dust ejected with a lower velocity and jets with a faster and more colimated emission. From our model, we derived dust mass production rates for different compositional grain types, amounting to at least 28 kg s –1 . Previously, salt-rich dust was believed to dominate the plume mass based on E5 data alone. The E17 profile shows a dominance of organic-enriched grains over the south polar terrain, a region not well constrained by E5 data. By including both E5 and E17 profiles, we find the salt-rich dust contribution to be at most 1% by mass. This revision also results from an improved understanding of grain masses of various compositional types that implies smaller sizes for salt-rich grains. Our new model can predict grain numbers and masses for future mission detectors during plume traversals.

79 ASTRONOMY AND ASTROPHYSICS↗

The Size Evolution of Passive Galaxies: Observations From the Wide-Field Camera 3 Early Release Science Program

We present the size evolution of passively evolving galaxies at z approximately 2 identified in Wide-Field Camera 3 imaging from the Early Release Science program. Our sample was constructed using an analog to the passive BzK galaxy selection criterion, which isolates galaxies with little or no ongoing star formation at z greater than approximately 1.5. We identify 30 galaxies in approximately 40 arcmin(sup 2) to H less than 25 mag. By fitting the 10-band Hubble Space Telescope photometry from 0.22 micrometers less than approximately lambda (sub obs) 1.6 micrometers with stellar population synthesis models, we simultaneously determine photometric redshift, stellar mass, and a bevy of other population parameters. Based on the six galaxies with published spectroscopic redshifts, we estimate a typical redshift uncertainty of approximately 0.033(1+z).We determine effective radii from Sersic profile fits to the H-band image using an empirical point-spread function. By supplementing our data with published samples, we propose a mass-dependent size evolution model for passively evolving galaxies, where the most massive galaxies (M(sub ∗) approximately 10(sup 11) solar mass) undergo the strongest evolution from z approximately 2 to the present. Parameterizing the size evolution as (1 + z)(sup - alpha), we find a tentative scaling of alpha approximately equals (−0.6 plus or minus 0.7) + (0.9 plus or minus 0.4) log(M(sub ∗)/10(sup 9 solar mass), where the relatively large uncertainties reflect the poor sampling in stellar mass due to the low numbers of highredshift systems. We discuss the implications of this result for the redshift evolution of the M(sub ∗)-R(sub e) relation for red galaxies.

fundamental parameters↗

Survey of Surveys: I. The largest compilation of radial velocities for the Galaxy

In the present-day panorama of large spectroscopic surveys, the amount, diversity, and complexity of the available data continuously increase. The overarching goal of studying the formation and evolution of our Galaxy is hampered by the heterogeneity of instruments, selection functions, analysis methods, and measured quantities. Here, we present a comprehensive catalogue, the Survey of Surveys (SoS), built by homogeneously merging the radial velocity (RV) determinations of the largest ground-based spectroscopic surveys to date, such as APOGEE, GALAH, Gaia-ESO, RAVE, and LAMOST, using Gaia as a reference. This pilot study serves to prove the concept and to test the methodology that we plan to apply in the future to the stellar parameters and abundance ratios as well. We have devised a multi-staged procedure that includes: (i) the cross match between Gaia and the spectroscopic surveys using the official Gaia cross-match algorithm, (ii) the normalisation of uncertainties using repeated measurements or the three-cornered hat method, (iii) the cross calibration of the RVs as a function of the main parameters on which depend (magnitude, effective temperature, surface gravity, metallicity, and signal-to-noise ratio) to remove trends and zero point offsets, and (iv) the comparison with external high-resolution samples, such as the Gaia RV standards and the Geneva-Copenhagen survey, to validate the homogenisation procedure and to calibrate the RV zero-point of the SoS catalogue. We provide the largest homogenised RV catalogue to date, containing almost 11 million stars, of which about half come exclusively from Gaia and half in combination with the ground-based surveys. We estimate the accuracy of the RV zero-point to be about 0.16–0.31 km s –1 and the RV precision to be in the range 0.05–1.50 km s –1 depending on the type of star and on its survey provenance. We validate the SoS RVs with open clusters from a high resolution homogeneous samples and provide the systemic velocity of 55 individual open clusters. Additionally, we provide median RVs for 532 clusters recently discovered by Gaia data. The SoS is publicly available and ready to be applied to various research projects, such as the study of star clusters, Galactic archaeology, stellar streams, or the characterisation of planet-hosting stars, to name a few. We also plan to include survey updates and more data sources in future versions of the SoS.

79 ASTRONOMY AND ASTROPHYSICS↗

DAmodel: hierarchical Bayesian modelling of DA white dwarfs for spectrophotometric calibration

We use hierarchical Bayesian modelling to calibrate a network of 32 all-sky faint DA white dwarf (DA WD) spectrophotometric standards (⁠16.5 < V , 19.5⁠) alongside three CALSPEC standards, from 912 Å to 32 μm. The framework is the first of its kind to jointly infer photometric zero points and WD parameters (surface gravity log g⁠, effective temperature T eff ⁠, extinction A V ⁠, dust relation parameter R V ) by simultaneously modelling both photometric and spectroscopic data. We model panchromatic Hubble Space Telescope Wide Field Camera 3 (HST/WFC3) UVIS and IR photometry, HST/STIS UV spectroscopy, and ground-based optical spectroscopy to sub-per cent precision. Photometric residuals for the sample are the lowest yet yielding < 0.004 mag RMS on average from the UV to the NIR, achieved by jointly inferring time-dependent changes in system sensitivity and WFC3/IR count-rate nonlinearity. Our GPU-accelerated implementation enables efficient sampling via Hamiltonian Monte Carlo, critical for exploring the high-dimensional posterior space. The hierarchical nature of the model enables population analysis of intrinsic WD and dust parameters. Inferred spectral energy distributions from this model will be essential for calibrating the James Webb Space Telescope as well as next-generation surveys, including Vera Rubin Observatory’s Legacy Survey of Space and Time and the Nancy Grace Roman Space Telescope.

methods: statistical↗

Comparative analysis of atmospheric parameters from high-resolution spectroscopic sky surveys: APOGEE, GALAH, Gaia -ESO

SDSS-IV APOGEE-2, GALAH, and Gaia-ESO are high-resolution, ground-based, multi-object spectroscopic surveys providing fundamental stellar atmospheric parameters and multiple elemental abundance ratios for hundreds of thousands of stars of the Milky Way. Data from these and other surveys contribute to investigations of the history and evolution of the Galaxy. We undertake a comparison between the most recent data releases of these surveys to investigate the accuracy and precision of derived parameters by placing the abundances on an absolute scale. We also discuss the correlations in parameter and abundance differences as a function of main parameters. Uncovering the variants provides a basis to continue the efforts of future sky surveys. Quality samples from the APOGEE-GALAH (15 537 stars), APOGEE-GES (804 stars), and GALAH-GES (441 stars) overlapping catalogs were collected. We investigated the mean variants between the surveys, and linear trends were also investigated. We compared the slope of correlations and mean differences with the reported uncertainties. The average and scatter of v rad , T eff , log g, [M/H], and v micro , along with numerous species of elemental abundances in the combined catalogs, show that in general there is a good agreement between the surveys. We find large radial velocity scatters ranging from 1.3 km s -1 to 4.4 km s -1 when comparing the three surveys. We observe some weak trends (e.g., in ΔT eff vs. Δlog g for the APOGEE-GES stars) and a clear correlation in the v micro - Δv micro planes in the APOGEE-GALAH common sample. For [α/H], [Ti/H] (APOGEE-GALAH giants), and [Al/H] (APOGEE-GALAH dwarfs) potential strong correlations are discovered as a function of the differences in the main atmospheric parameters, and we also find weak trends for other elements. In general we find good agreement between the three surveys within their respective uncertainties. However, there are certain regimes in which strong variants exist, which we discuss. There are still offsets larger than 0.1 dex in the absolute abundance scales.

79 ASTRONOMY AND ASTROPHYSICS↗

From Fundamental Interfacial Reaction Kinetics to Macroscopic Current–Voltage Characteristics: Case Study of Solid Acid Fuel Cell Limitations and Possibilities

The unique properties of solid acid electrolytes, in particular CsH 2 PO 4 , are in many ways ideal for fuel cell operation. However, the technology is constrained by high cathode overpotentials. Here a simplified cathode geometry is employed to obtain the fundamental electrochemical parameters (exchange current density and charge transfer coefficient) describing the oxygen reduction reaction (ORR) at the CsH 2 PO 4 -Pt-gas interface. The parameters are incorporated into a 1D model of the voltage–current characteristics of realistic SAFC cathodes, which reproduced the measured polarization behavior of such cathodes without recourse to fitting adjustable parameters. Following this validation, the model is utilized to evaluate the impact of changes to cathode properties, microstructure, and operating conditions. Of these, the charge transfer coefficient, measured to have a value of ≈0.6 for ORR on Pt in the SAFC cathode environment, is found to have the greatest impact on power output. Nevertheless, even without material modifications, a combination of microstructural and operational modifications are identified with projected performance metrics meeting Department of Energy targets (0.8 V at 300 mA cm –2 , and peak power density of 1 W cm –2 ), albeit at high Pt loadings. However, the analysis indicates that truly meaningful advances will likely necessitate the discovery of alternative ORR catalysts.

36 MATERIALS SCIENCE↗

Evolution of the Electronic Gap of Directly Synthesized Versus Mechanically Transferred WS 2 Monolayer to Multilayer Films

The electronic properties of 2D materials play a critical role in determining their potential for device applications. Despite rapid developments in 2D semiconductors, studies of fundamental electronic parameters, including the electronic gap and ionization energy, are limited, with significant discrepancies in reported values. The study focuses on tungsten disulfide (WS₂) and investigates the electronic structure of films comprising an increasing number of layers deposited with two different methods: direct synthesis via metal–organic chemical vapor deposition (MOCVD) and additive mechanical transfer of exfoliated single layers. The films are characterized via Raman, UV–vis, and photoluminescence spectroscopies, as well as ultraviolet photoelectron and inverse photoemission spectroscopies (UPS/IPES). The electronic gap of WS₂ is found to decrease from 2.43 eV for the monolayer to 1.97 eV for the trilayer, indicating a bulk transition at the trilayer thickness. This reduction in the electronic gap is primarily due to the downward shift of the conduction band minimum relative to the valence band maximum. A comparative analysis with MOCVD-grown WS₂ reveals a slightly larger electronic gap for MOCVD-grown samples, attributed to differences in defect densities. The electronic levels evaluated through UPS/IPES highlight the significant influence of preparation methods on the electronic properties of WS₂.

2D materials↗

High‐Order Nonlinear Frequency Conversion in Transparent Conducting Oxide Thin Films

The study of conductive oxides has gained momentum within the photonics community due to their unique linear and nonlinear optical properties. Despite recent experiments reporting on high harmonic generation from thin films, the optical/electronic behavior of these compounds at the nanoscale is still not fully understood due to the lack of a suitable theoretical model. In the present work, aluminum zinc oxide is excited near its epsilon-near-zero crossing point using incident femtosecond pulses having peak power densities in the 1 TW cm −2 range. A relatively efficient frequency up-conversion including even and odd harmonics up to the seventh order is observed. A hydrodynamic-Maxwell theoretical approach is adopted, capable of simultaneously taking into account linear and nonlinear dispersions, nonlocal effects, surface, magnetic, and bulk nonlinearities in a spectral region that spans over two and a half octaves from the UV to the NIR region. The study enables a deeper understanding of the fundamental material parameters regulating optical nonlinearities, providing important insights to engineer this class of materials for applications in sensing, ultra-fast physics, and spectroscopy.

material modeling↗

A heavy QCD axion and the mirror world

We study the mirror world with dark matter arising from the thermal freeze-out of the lightest, stable mirror particle — the mirror electron. The dark matter abundance is achieved for mirror electrons of mass 225 GeV, fixing the mirror electroweak scale near 10 8 GeV. This highly predictive scenario is realized by an axion that acts as a portal between the two sectors through its coupling to the QCD and mirror QCD sectors. The axion is more massive than the standard QCD axion due to additional contributions from mirror strong dynamics. Still, the strong CP problem is solved by this ‘heavy’ axion due to the alignment of the QCD and mirror QCD potentials. Mirror entropy is transferred into the Standard Model sector via the axion portal, which alleviates overproduction of dark radiation from mirror glueball decays. This mirror scenario has a variety of signals: (1) primordial gravitational waves from the first-order mirror QCD phase transition occurring at a temperature near 35 GeV, (2) effects on large-scale structure from dark matter self-interactions from mirror QED, (3) dark radiation affecting the cosmic microwave background, and (4) the rare kaon decay, K + → (π + + axion). The first two signals do not depend on any fundamental free parameters of the theory while the latter two depend on a single free parameter, the axion decay constant.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Optical and mass-spectral characterization of mixed-gas flowing atmospheric-pressure afterglow sources

Plasma-based ambient desorption/ionization (ADI) sources for mass spectrometry (MS) often use helium as the primary discharge gas due to the large reaction cross section of excited helium species with atmospheric gases, which ultimately leads to efficient reagent-ion formation. However, some studies have shown that mixed-gas plasmas provide unique advantages. For instance, our group showed that a helium-oxygen flowing atmospheric-pressure afterglow (He:O 2 -FAPA) source yielded enhanced ion signals for small polar analytes, but compounds with aromatic rings underwent chemical modification to produce pyrylium species. Here, it is shown that the addition of H 2 to the helium FAPA gas significantly decreased the reagent-ion signals, but analyte-ion signal was not affected to the same degree. In addition, mass spectra obtained with He:H 2 -FAPA were chemically cleaner with fewer ions stemming from analyte species and produced less oxidation of analytes. Addition of nitrogen increased the abundance of negative reagent ions (e.g., NO 2 - and NO 3 - ) which led to enhanced ion signal for RDX. To better understand these unique advantages of a mixed-gas FAPA, the impact of molecular-gas (O 2 , N 2 , or H 2 ) addition on the optical-emission spectra from the discharge was also measured. Spatially resolved emission was obtained from the anode- and negative-glow regions. In general, addition of small fractions (~0.1%) of molecular gases decreased helium and OH emission intensities. Atomic oxygen and hydrogen emission increased with the addition of O 2 and H 2 , respectively. Furthermore, emission characteristics of N 2 , N 2 + , and NO with respect to molecular gas composition on He-FAPA were measured. Finally, fundamental plasma parameters, such as OH rotational temperature (T rot ), were also calculated for these mixed-gas systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Identification and properties of isolated field elliptical galaxies from CFHTLS-W1

We present a catalogue of isolated field elliptical (IfE) galaxies drawn from the W1 field of the Canada-France-Hawaii Telescope Legacy Survey (CFHTLS). 228 IfEs were identified from a flux-limited (r < 21.8) galaxy catalogue which corresponds to a density of 3 IfE/sq.deg. For comparison we consider a sample of elliptical galaxies living in dense environments, based on identification of the brightest cluster galaxies (BGCs) in the same survey. Using the same dataset for the comparison sample ensures a uniform selection, including in the redshift range as IfEs (i.e. 0.1 < z <0.9). A comparison of elliptical galaxies in different environments reveals that IfEs and BCGs have similar behaviours in their colours, star formation activities, and scaling relations of mass–size and size–luminosity. IfEs and BCGs have similar slopes in the scaling relations with respect to cluster ellipticals within the $ -24 \leq M_{r} \leq -22 $ magnitude and $10.2 < \textrm{log}(M_{*}/ \textrm M_\odot)\leq12.0 $ mass ranges. Three IfEs identified in this study can be associated with fossil groups found in the same survey area which gives clues for future studies.

79 ASTRONOMY AND ASTROPHYSICS↗

Chemical Challenges that the Peroxide Dianion Presents to Rechargeable Lithium–Air Batteries

Understanding the fundamental redox reactions and processes that occur in lithium–air and, more generally, metal–air batteries is important to the progress of this promising energy-storage technology. Knowledge of the chemistry of the peroxide dianion, O 2 2– , is especially crucial, as the dianion is at the nexus of the charge/discharge cycle of lithium–air batteries. The intrinsic electron transfer properties and redox chemistry of peroxide dianion are poorly defined because it is difficult to isolate the dianion free of protons and metal ions. We review the results of (i) the electron transfer kinetics and (ii) the redox reaction chemistry of isolated peroxide dianion encapsulated within the cavity of a hexacarboxamide cryptand. With regard to the former, electron transfer kinetics measurements provide fundamental Marcus parameters that will be useful for models that seek to disentangle the precise contributions of Li + ion-coupled electron transfer, electron transfer across the Li 2 O 2 solid particle interface, and charge hopping among Li 2 O 2 particles. With regard to the latter, an underappreciated chemistry of peroxide dianion with CO 2 produces peroxymonocarbonate (OOCO 2 2– ) and peroxydicarbonate (O 2 COOCO 2 2– ). An autocatalytic cycle will lead to oxidative degradation of traditional organic electrolytes and other vulnerable cell components employed in lithium–air batteries. Furthermore, this peroxycarbonate-derived chemistry, in addition to more commonly recognized solution-based oxidation chemistry, will need to be mitigated to realize the long-term cyclability of rechargeable lithium–air batteries.

25 ENERGY STORAGE↗

Quantifying Charge Carrier Localization in PBTTT Using Thermoelectric and Spectroscopic Techniques

Chemically doped poly[2,5-bis(3-alkylthiophen-2-yl)thieno[3,2- b ]thiophene] (PBTTT) shows promise for many organic electronic applications, but rationalizing its charge transport properties is challenging because conjugated polymers are inhomogeneous, with convoluted optical and solid-state transport properties. Herein, we use the semilocalized transport (SLoT) model to quantify how the charge transport properties of PBTTT change as a function of iron(III) chloride (FeCl 3 ) doping level. We use the SLoT model to calculate fundamental transport parameters, including the carrier density needed for metal-like electrical conductivities and the position of the Fermi energy level with respect to the transport edge. We then contextualize these parameters with other polymer-dopant systems and previous PBTTT reports. Additionally, we use grazing incidence wide-angle X-ray scattering and spectroscopic ellipsometry techniques to better characterize inhomogeneity in PBTTT. Our analyses indicate that PBTTT obtains high electrical conductivities due to its quickly rising reduced Fermi energy level, and this rise is afforded by its locally high carrier densities in highly ordered microdomains. Ultimately, this report sets a benchmark for comparing transport properties across polymer-dopant-processing systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electron Beam Infrared Nano-Ellipsometry of Individual Indium Tin Oxide Nanocrystals

Leveraging recent advances in electron energy monochromation and aberration correction, we record the spatially resolved infrared plasmon spectrum of individual tin-doped indium oxide nanocrystals using electron energy-loss spectroscopy (EELS). Both surface and bulk plasmon responses are measured as a function of tin doping concentration from 1–10 atomic percent. Furthermore, these results are compared to theoretical models, which elucidate the spectral detuning of the same surface plasmon resonance feature when measured from aloof and penetrating probe geometries. We additionally demonstrate a unique approach to retrieving the fundamental dielectric parameters of individual semiconductor nanocrystals via EELS. This method, devoid from ensemble averaging, illustrates the potential for electron-beam ellipsometry measurements on materials that cannot be prepared in bulk form or as thin films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CH 4 Activation over Perovskite Catalysts: True Density and Reactivity of Active Sites

The high thermal stability of perovskites has drawn attention toward their applications for catalytic CH 4 activation and conversion, typically occurring at high temperatures. The reaction rates of perovskite catalysts for CH 4 combustion, however, trail behind those of noble metal catalysts. Ways to optimize the performance of perovskite catalysts are destined to trial-and-error approaches unless their complex reconstructed surfaces are correlated with fundamental kinetic parameters. Discerning the intrinsic activity of surface catalytic sites and the density of those sites is crucial to rationally envision complex metal oxides with enhanced catalytic performance. Here, the present work presents a detailed kinetic analysis of catalytic CH 4 combustion over a set of seven perovskites (SrTiO 3 , SrZrO 3 , SrFeO 3 , LaFeO 3 , LaInO 3 , LaCoO 3 , LaMnO 3 ) with various surface terminations. Steady-state isotopic transient kinetic analysis was employed to measure turnover frequency (TOF) and density of surface intermediates (N) under operando conditions. Top surface characterization elucidated performance-structure relationships between near-monolayer surface composition and intrinsic reactivity of the catalysts. By using a chemical etching procedure to expose Fe-sites at the top surface of LaFeO 3 (LaFeO 3 , HNO 3 ), its TOF was increased 4-fold, compared with the unmodified sample, although N on the surface of LaFeO 3 , HNO 3 decreased. Density functional theory simulations corroborated that surface Fe-termination and La-Fe termination offer lower energetic barriers for CH 4 activation when compared with La-termination. In general, surface reconstruction is shown as a tool to tune TOF and N to improve reaction rates. This work fills a gap in current kinetic studies of perovskites through a careful assessment and discussion of the density and intrinsic reactivity of active sites for methane combustion over well-characterized reconstructed perovskite surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗