Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “frequency transform”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 433 records · Page 24

Efficient Detection of Emission-line Galaxies in the Cl0016+1609 and MACSJ1621.4+3810 Supercluster Filaments Using SITELLE

We observe a system of filaments and clusters around Cl0016+1609 and MACSJ1621.4+3810 using the SITELLE Fourier transform spectrograph at the Canada–France–Hawaii Telescope. For Cl0016+1609 (z = 0.546), the observations span an 11.8 Mpc × 4.3 Mpc region along an eastern filament that covers the main cluster core, as well as two 4.3 Mpc × 4.3 Mpc regions that each cover southern subclumps. For MACSJ1621.4+3810 (z = 0.465), 3.9 Mpc × 3.9 Mpc around the main cluster core is covered. We present the frequency and location of the emission-line galaxies and their emission-line images, and calculate the star formation rates, specific star formation rates, and merger statistics. In Cl0016+1609, we find 13 [O ii] 3727 Å emitting galaxies with star formation rates between 0.2 and 14.0 M {sub ⊙} yr{sup −1}. Of these, 91{sub −10}{sup +3}% are found in regions with moderate local galaxy density, avoiding the dense cluster cores. These galaxies follow the main filament of the superstructure and are mostly blue and disky, with several showing close companions and merging morphologies. In MACSJ1621.4+3810, we find 10 emission-line sources. All are blue (100{sub −15}{sup +0}%), with 40{sub −12}{sup +16}% classified as disky and 60{sub −16}{sup +12}% as merging systems. Eight avoid the cluster core (80{sub −17}{sup +7}%), but two (20{sub −7}{sup +17}%) are found near high-density regions, including the brightest cluster galaxy (BCG). These observations push the spectroscopic study of galaxies in filaments beyond z ∼ 0.3 to z ∼ 0.5. Their efficient confirmation is paramount to their usefulness as more galaxy surveys come online.

47 OTHER INSTRUMENTATION↗

Holographic Nano‐Imaging of Terahertz Dirac Plasmon Polaritons in Topological Insulator Antenna Resonators

Abstract Excitation of Dirac plasmon polaritons (DPPs) in bi‐dimensional materials have attracted considerable interest in recent years, both from perspectives of understanding their physics and exploring their transformative potential for nanophotonic devices, including ultra‐sensitive plasmonic sensors, ultrafast saturable absorbers, modulators, and switches. Topological insulators (TIs) represent an ideal technological platform in this respect because they can support plasmon polaritons formed by Dirac carriers in the topological surface states. Tracing propagation of DPPs is a very challenging task, particularly at terahertz (THz) frequencies, where the DPP wavelength becomes over one order of magnitude shorter than the free space photon wavelength. Furthermore, severe attenuation hinders the comprehensive analysis of their characteristics. Here, the properties of DPPs in real TI‐based devices are revealed. Bi 2 Se 3 rectangular antennas can efficiently confine the propagation of DPPs to a single dimension and, as a result, enhance the DPPs visibility despite the strong intrinsic attenuation. The plasmon dispersion and loss properties from plasmon profiles are experimentally determined, along the antennas, obtained using holographic near‐field nano‐imaging in a wide range of THz frequencies, from 2.05 to 4.3 THz. The detailed investigation of the unveiled DPP properties can guide the design of novel topological quantum devices exploiting their directional propagation.

Chemistry↗

Efficient generation of the 7th harmonic of Ti:sapphire (114.6 nm) vacuum ultraviolet pulses with 60 fs duration by non-collinear four-wave mixing in argon

The recent advances in femtosecond vacuum UV (VUV) pulse generation, pioneered by the work of Noack et al., has enabled new experiments in ultrafast time-resolved spectroscopy. Expanding on this work, we report the generation of 60 fs VUV pulses at the 7th harmonic of Ti:sapphire with more than 50 nJ of pulse energy at a repetition rate of 1 kHz. Additionally, the 114.6 nm pulses are produced using non-collinear four-wave difference-frequency mixing in argon. The non-collinear geometry increases the phase-matching pressure, and results in a conversion efficiency of ~10-3 from the 200 nm pump beam. The VUV pulses are pre-chirp-compensated for material dispersion with xenon, which has negative dispersion in this wavelength range, thus allowing almost transform-limited pulses to be delivered to the experimental chamber.

36 MATERIALS SCIENCE↗

TX$^2$: Transformer eXplainability and eXploration

The Transformer eXplainability and eXploration (Martindale & Stewart, 2021), or TX 2 software package, is a library designed for artificial intelligence researchers to better understand the performance of transformer models (Vaswani et al., 2017) used for sequence classification. The tool is capable of integrating with a trained transformer model and a dataset split into training and testing populations to produce an ipywidget (Project Jupyter Contributors, 2021) dashboard with a number of visualizations to understand model performance with an emphasis on explainability and interpretability. The TX 2 package is primarily intended to integrate into a workflow centered around Jupyter Notebooks (Kluyver et al., 2016), and currently assumes the use of PyTorch (Paszke et al., 2019) and Hugging Face transformers library (Wolf et al., 2020). The dashboard includes visualization and data exploration features to aid researchers, including an interactive UMAP embedding graph (McInnes et al., 2018) to understand classification clusters, a word salience map that can be updated as researchers alter textual entries in near real time, a set of tools to understand word frequency and importance based on the clusters in the UMAP embedding graph, and a set of traditional confusion matrix analysis tools.

97 MATHEMATICS AND COMPUTING↗

Time-domain Brillouin scattering theory for probe light and acoustic beams propagating at an angle and acousto-optic interaction at material interfaces

A theory has been developed to interpret time-domain Brillouin scattering (TDBS) experiments involving coherent acoustic pulse (CAP) and light pulse beams propagating at an angle to each other. It predicts the influence of the directivity pattern of their acousto-optic interaction on TDBS signals when heterodyne detection of acoustically scattered light is in backward direction to incident light. The theory reveals relationships between the carrier frequency, amplitude and duration of acoustically induced ”wave packets” in light transient reflectivity signals, and factors such as CAP duration, widths of light and sound beams, and their interaction angle. It describes the transient dynamics of these wave packets when the light and CAP encounter material interfaces, and how the light scattering by the incident CAP transforms into scattering by the reflected and transmitted CAPs. The theory suggests that single-point TDBS experiments can determine not only depth positions of buried interfaces but also their local inclinations/orientations.

42 ENGINEERING↗

Postfire Biogeochemical Processes: Implications to Source Water Quality in Fire-Influenced Watersheds

Forested watersheds are instrumental in providing purified and reliable water to millions of people worldwide. The changing climate has increased the frequency and severity of global fire events. Forested watersheds and their ecosystem functions are greatly disrupted during fire activity. Postfire concerns in forested watersheds include unpredictable and potentially simultaneous alterations in source water quality and hydro-biogeochemical processes. Here, the degree of fire severity can complexly modify water quality through the production of fire-transformed constituents on the burned forest floor (i.e., nutrients, metal(loid)s, dissolved organic matter, and the formation of disinfection byproducts). Correspondingly, fire severity and postfire rainfall patterns can refine hydro-biogeochemical processes that influence the transport of the fire-transformed constituents (i.e., vegetation function, soil structure, hydrological pathways, and microbial communities). Postfire alterations to water quality and hydro-biogeochemical processes introduce further complexity with varying temporal influence, which ranges from months to decades. As postfire water quality and watershed response research progresses, it is essential to homogenize interdisciplinary expertise to bridge knowledge gaps between fields ranging from forest ecology, hydrology, microbiology, and geochemistry. A multidisciplinary approach in wildfire research will facilitate a comprehensive perception of the diverse water quality risks associated with fire activity and mitigate fire concerns on a global level.

Disinfection Byproducts↗

Universal Passive Synchronization Method for Grid-Forming Inverters Without Mode Transition

Power systems are transforming with increasing levels of inverter-based resources (IBRs). This transformation requires critical roles of grid-forming (GFM) inverters replacing synchronous generators for bulk power system stabilization and ancillary services, also allowing flexible power system operation, such as microgrid that is operated by multiple GFM IBRs to achieve system resilience against contingencies. To realize the resilient power systems allowing flexible in-and-out operation of GFM IBRs potentially programmed with different primary controls, a synchronization method universally applicable, i.e., independent of control types, would be beneficial to ease the integration process, but it has not been actively studied. To fill the gap, this paper proposes a universal synchronization method that achieves a passive synchronization to enable a smooth transition in a grid with off-nominal system parameters, i.e., voltage and frequency. The logic proposed requires no modification on the primary control, thus applicable to any type of GFMs with a voltage reference input. To validate the concept, a simulation of an IEEE 13-bus benchmark system modified with 3 GFM inverters is presented. It simulates an inverter-driven black start scenario in which GFM inverters autonomously turn on and connect to the grid under heavy loading, using the synchronization logic. The case study demonstrates that GFM inverters can tune their voltage reference to smoothly synchronize without severe transients, and contribute to a seamless black start of the grid under unbalanced load conditions. Two GFM methods - Droop and dispatchable virtual oscillator control - are used for the demo to validate feasibility and interoperability of the passive synchronization.

black start↗

Broadband coplanar-waveguide-based impedance-transformed Josephson parametric amplifier

Quantum-limited Josephson parametric amplifiers play a pivotal role in advancing the field of circuit quantum electrodynamics by enabling the fast and high-fidelity measurement of weak microwave signals. Therefore, it is necessary to develop robust parametric amplifiers with low noise, broad bandwidth, and reduced design complexity for microwave detection. However, current broadband parametric amplifiers either have degraded noise performance or rely on complex designs. Here, we present a device based on the broadband impedance-transformed Josephson parametric amplifier that integrates a hornlike coplanar waveguide transmission line, which significantly decreases the design and fabrication complexity while keeping comparable performance. The device shows an instantaneous bandwidth of 700 (200) MHz for 15 (20) dB gain with an average input saturation power of − 110 dBm and near quantum-limited added noise. The operating frequency can be tuned over 1.4 GHz using an external flux bias. We further demonstrate the negligible backaction from our device on a transmon qubit. The amplification performance and simplicity of our device promise its wide adaptation in quantum metrology, quantum communication, and quantum information processing. Published by the American Physical Society 2024

Qing, Bingcheng (ORCID:0000000345227017)↗

Evaluation of Zero-Net-Rate Pumping Tests

Accurately estimating the distribution of aquifer properties is key to understanding contaminant movement in the subsurface. The distribution of aquifer properties is typically addressed using slug or constant-rate well tests, and the pros and cons of these tests are well known. Slug tests are appealing because they avoid removing contaminated water, but their results are affected by well skin and the small volume of displaced water limits the volume of aquifer that can be evaluated. Constant-rate well tests have the disadvantage of requiring disposal of potentially contaminated water, but they can generate properties that are more representative than slug tests, and they can be used to estimate well efficiency and storativity, which are difficult to characterize using slug tests. Periodic pumping tests are appealing because they have many of the advantages and few of the disadvantages of slug and constant-rate well tests. Periodic pumping tests involve cycling the pumping rate with a regular period and measuring the resulting response in monitoring wells. Some of these tests involve imposing a periodic rate on a constant mean rate. However, other tests involve moving water out and back into the well at rates that are balanced so the net rate after each period is zero. Some zero-net-rate (ZNR) well tests use rates that follow a sinusoidal pattern, whereas others use a square wave pattern that switches between a constant rate of pumping and a constant rate of injection to achieve a zero-net rate. ZNR well tests appear to be a useful compromise between slug and constant rate tests, but methods for conducting and analyzing the results from these tests have received limited evaluation. Periodic pumping tests are typically evaluated through recorded pressure responses to a disturbance source. Recent work has demonstrated that the strain field in the vadose zone shows a response to disturbances in the underlying aquifer. Various instrument designs are available that can record vertical and horizontal strain to very precise resolutions (10-9 ε). Measuring the strain in the vadose zone can present lower costs than measuring pressure in a monitoring well, so using strain could improve the resolution of ZNR tests, as well as make these tests potentially cheaper. A ZNR periodic pumping system was constructed and used to perform tests in the Clemson, South Carolina area. The system was designed to pump and inject with a periodic square-wave, so pumping occurs at a constant rate for half the period and is followed by injection at the same rate for half the period resulting in no net gain or loss of water from the aquifer. The system is designed to generate flow rates from 1 to 3.5 gallons per minute (gpm) with a capacity of 875-gallon per half period. Pressure and strain monitoring points are located in the vicinity of the pumping well. A series of 10 ZNR periodic pumping tests were conducted at the field site, with periods ranging from 2 to 540 minutes. Pressure data were collected and recorded in four monitoring wells in various locations around the pumping well. In addition, vertical and horizontal strain and tilt data were recorded in various locations around the pumping well. Traditional aquifer tests, including slug tests and constant-rate pumping tests were conducted at the field site to provide a baseline of aquifer parameter estimates that are compared the results of ZNR tests. Pressure data measured at monitoring wells during ZNR tests were analyzed utilizing an analytical solution (Streltsova, 1988) that assumes a confined aquifer and estimates hydraulic diffusivity and transmissivity using the time lag and amplitude of the pressure signal. The storativity can be separated out from the hydraulic diffusivity using the transmissivity estimate. The time-lag and amplitude of the pressure signals were estimated using a Fourier transform. The time-lag of the primary period of the pressure increases as a linear function of distance from the pumping well, and it increases as the square root of the period of the ZNR test over a range of periods spanning two orders of magnitudes. The first few harmonics follow similar trends, but the higher frequency harmonics diverge from this trend. Strain and tilt data from various instruments in the vadose and saturated zones are periodic during ZNR tests. The time lags of the strain components increase roughly linearly with distance from the well. Many of the time lags of the strain data from the vadose zone are similar to the time lags observed in the pressure data from a similar distance and pumping period. Theoretical experiments were performed to understand how pressure and strain responds to ZNR periodic pumping. The time-lags of the simulated pressure responses match the field data trends. The results were used to validate the Streltsova (1988) solution for periodic pumping to estimate hydraulic diffusivity. Hydraulic diffusivity was estimated to be 1.8 x 10-2 m2s-1 < Dh < 9.0 x 10-2 m2s-1 using pressure data from all the wells during ZNR tests. Transmissivity was estimated to be 0.8 x 10-4 m2s-1 < T < 4.3 x 10-4 m2s-1. Assuming Storativity = T/Dh gives 1.1 x 10-3 < S < 19 x10-3. Transmissivity is used to estimate the hydraulic conductivity, K, by dividing by the assumed aquifer thickness. Two constant-rate pumping tests were conducted and analyzed using two conceptual models: The Hantush (1961) solution was used to analyze data assuming confined conditions and the Neuman (1974) solution was used to analyze data assuming unconfined conditions. The Hantush (1961) solution estimated transmissivity to be 1.6 x 10-4 m2s-1 < T < 1.8 x 10-4 m2s-1 when using data from all the wells. Storativity was estimated to be 4.4 x 10-3 < S < 8.2 x 10-3. Assuming Dh = T/S gives 0.22 x 10-2 m2s-1 < Dh < 3.6 x 10-2 m2s-1. The Neuman (1974) solution estimated transmissivity to be 0.80 x 10-4 m2s-1 < T < 0.84 x 10-4 m2s-1. Total storativity (S + Sy) was estimated to be 22 x 10-3 < S < 110 x 10-3. Storativity excluding the Sy term was estimated to be 2.2 x 10-3 < S < 2.5 x 10-3. Assuming Dh = T/S gives 0.073 x 10-2 m2s-1 < S < 0.36 x 10-2 m2s-1. Two slug tests were performed on the pumping well, PW-2. The Bouwer and Rice (1976) solution for slug tests was used to analyze the data. This solution works for both confined and unconfined conditions, so both conceptual models were covered through the analysis. Hydraulic conductivity was estimated to be 1.95 x 10-6 ms-1 < K < 2.49 x 10-6 ms-1. Statistical comparison show generally no significant difference in the estimates of Dh, K, or S made using ZNR and conventional pumping tests.. However, the total storage estimated by the Neuman (1974) solution for unconfined settings is larger than that estimate using the Streltsove analysis applied to the ZNR tests. This is likely because the Neuman solution considers delayed yield from storage that the water table, whereas the Streltsova (1988) solution assumes confined conditions. The analysis also indicates that there is a statistically significant difference between parameters estimated with conventional slug tests and those measured with either constant-rate pumping tests or ZNR tests. Hydraulic diffusivity is estimated from the time-lag and the distance from the well. The time-lags of the strain data from the vadose zone are similar to the lags of the pressure data from a similar distance. This indicates that hydraulic diffusivities estimated from the strain data measured in the vadose zone would be similar to the estimates from the pressure data measured in the aquifer. There appear to be sign reversals in some of the strain data that were corrected to estimate the time lag. The dissolved oxygen (CO) concentration was measured during several ZNR tests to evaluate the feasibility of using the procedure to increase contaminant degradation kinetics that are related to DO. The results indicate that DO can be increased during the cycling of ZNR tests in some cases.

Smith-Jones, Austin↗

Recursive Use of the Short-Time Fast Fourier Transform for Signature Analysis in Continuous Processes

Although a nuclear reactor is a hostile environment for sensing and electrical communications, the reactor core is amenable to acoustic communication. An acoustic measurement infrastructure (AMI) has been installed in the Advanced Test Reactor (ATR) to record acoustic signals that can capture its different operating regimes. AMI uses coolant pumps as continuous signal sources, coolant and structural components as transmission lines, and accelerometers to capture system motion. A recursive signal processing technique based on the short-time fast Fourier transform (STFFT) for continuous processes provides unique signatures for diagnostic and prognostic analyses from the system motion data. Here this article presents a recursive STFFT methodology that processes acoustic signals from continuous industrial processes. The article first discusses the initial STFFT use with simulated data to elucidate the basic principles necessary to understand and interpret the STFFT results from actual pump vibration data. Each repetitive use of the STFFT on pump vibration data using the results from the prior STFFT processing will generate additional complimentary time-frequency-based signatures. These signatures are generated by the coolant pumps operating under different process conditions. After each use of the STFFT, the resulting signatures provide exemplary examples of the diversity and intuitive nature of recursively using the STFFT. This article focuses on recursively using the STFFT to provide numerous complimentary and diverse signatures that will ultimately be inputs for machine learning algorithms that provide predictive data analytics. The intuitive nature of the information and signatures from recursive STFFT processing will also bring intuitive interpretation capabilities to machine learning and predictive data analytic techniques.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Leveraging SETS resilience capabilities for safe-to-fail infrastructure under climate change

As the rehabilitation of infrastructure is outpaced by changes in the profile, frequency, and intensity of extreme weather events, infrastructure’s service disruptions and failures become increasingly likely. Safe-to-fail approaches for infrastructure planning and design improve the capacity of cities to adapt for uncertain climate futures by identifying social, ecological, and technological systems (SETS) capabilities to prepare for potential failure scenarios. In this work, we argue for transforming infrastructure planning and design to effectively utilize safe-to-fail approaches by navigating the opportunities and trade-offs of SETS resilience capabilities. From a technological vantage point, traditional infrastructure planning approaches account for social and ecological domains as external design conditions rather than embedded system characteristics. Safe-to-fail approaches directly challenge the isolation of the technological domain by necessitating a recognition that SETS domains are interconnected and interdependent in infrastructure systems, as such risks and system capabilities for resilience must be managed cohesively.

54 ENVIRONMENTAL SCIENCES↗

Effect of Density Irregularities on Radio Frequency Wave Propagation in Ionospheric Plasmas

Density irregularities play a vital role in determining how radio frequency (RF) waves travel through plasmas. In the Earth’s ionosphere, these density irregularities also impact radio communication. In this study, we conduct a detailed numerical analysis of RF wave propagation in small-scale ionospheric density irregularities using the advanced Petra-M code. We focus specifically on high-frequency (HF) waves, ranging from 3 to 30 MHz, which are essential for military, amateur radio operators, and emergency communications. By introducing density structures, such as equatorial plasma bubbles derived from fluid simulations, we demonstrate that HF waves can scatter in multiple directions when they encounter these irregularities. Additionally, we observe significant mode conversion, where incoming electromagnetic waves transform into electrostatic modes within the density gradient layer. This shows that smaller density irregularities can greatly weaken signals or cause complete signal loss for receivers, emphasizing the need for increased awareness and innovative solutions in radio communication transmission.

Kim, Eun-Hwa [Princeton Plasma Physics Laboratory ↗

Structural, magnetic, optical, dielectric and electronic properties of R 2 NiIrO 6 (R = Pr and Nd): A comprehensive experimental and theoretical investigation

Double perovskites are highly promising materials capable of exhibiting a wide variety of phenomena. In this work, we perform a comprehensive experimental and theoretical study of polycrystalline R 2 NiIrO 6 (R = Pr and Nd) compounds. Both compounds were synthesised using the solid-state reaction method. Rietveld refinement confirmed a monoclinic structure with the P2 1 /n space group for both compounds. The scanning electron images showed the average grain sizes of 0.55 μm for R = Pr and 0.46 μm for R = Nd. Fourier transform infrared ra- diation spectra of the two compounds presented two intense bands at 470 cm -1 and 540 cm -1 . The optical measurements revealed that the band gaps of the compounds were in the visible absorption range. The field- cooled magnetisation - field hysteresis measurements indicated exchange bias properties in the synthesised compounds at low temperatures. Both temperature and frequency variation of dielectric constant and loss tangent measurements were conducted. The frequency-dependent ac conductivity measurements indicated that the conductivity increases with the increase of frequency as well as temperature. The Nd 2 NiIrO 6 compound showed lower ac conductivities compared to its isostructural Pr 2 NiIrO 6 compound. The atomic and electronic structures of Nd 2 NiIrO 6 and Pr 2 NiIrO 6 were explored using the spin-polarised calculations performed within the DFT+U method. Our results suggested that the inclusion of on-site correlations and repulsions for the d-states of atoms was necessary in order to obtain finite band gaps of Nd 2 NiIrO 6 and Pr 2 NiIrO 6 systems.

36 MATERIALS SCIENCE↗

Mitigating spectral bias in neural operators via high-frequency scaling for physical systems

Neural operators have emerged as powerful surrogates for modeling complex physical problems. However, they suffer from spectral bias making them oblivious to high-frequency modes, which are present in multiscale physical systems. Therefore, they tend to produce over-smoothed solutions, which is particularly problematic in modeling turbulence and for systems with intricate patterns and sharp gradients such as multi-phase flow systems. In this work, we introduce a new approach named high-frequency scaling (HFS) to mitigate spectral bias in convolutional-based neural operators. By integrating HFS with proper variants of UNet, we demonstrate a higher prediction accuracy by mitigating spectral bias in single and two-phase flow problems. Unlike Fourierbased techniques, HFS is directly applied to the latent space, thus eliminating the computational cost associated with the Fourier transform. Additionally, we investigate alternative spectral bias mitigation through a diffusion model conditioned on neural operators. While the diffusion model integrated with the standard neural operator may still suffer from significant errors, these errors are substantially reduced when the diffusion model is integrated with a HFS-enhanced neural operator.

97 MATHEMATICS AND COMPUTING↗

Insights into the Structure–Activity Relationships in Metal–Organic Framework-Supported Nickel Catalysts for Ethylene Hydrogenation

Solid supports play an indispensable role in heterogeneous catalysis, as they can directly affect the catalytic activity and selectivity of supported catalysts. However, the specific roles of such supports remain to be demystified owing to the difficulties in obtaining precise structural information on supported catalysts. To understand the effects of MOF topology, pore environment, and metal identity of node supports on the catalytic activity, a Ni catalyst was supported on eight Zr- or Hf-MOFs based on 8-connected nodes: namely M-NU-1200, M-NU-1000, M-NU-1008, and M-NU-1010 (M = Zr, Hf). Single-crystal X-ray diffraction (SCXRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and X-ray photoelectron spectroscopy (XPS) were employed to characterize the supported catalyst structures. To investigate the support effects on their activities, the supported Ni catalysts were evaluated by using ethylene hydrogenation as a model reaction. The results revealed that all Hf-based-MOF-supported Ni catalysts exhibited higher catalytic reactivity with TOF (turnover frequency) values at least double of those isostructural Zr counterparts. Additionally, MOFs with less congested metal anchoring sites, as a result of the topology and surrounding pore environment, yielded higher TOFs, suggesting the importance of supports in dictating both the catalyst accessibility and activity. Computational analysis complemented the experimental observations and provided insights into reaction barrier differences and their performance variation. Furthermore, this study demonstrates the essential role of the supports and provides a thought for selecting/designing suitable supports in heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Insights into the Promotion with Ru of Co/TiO 2 Fischer–Tropsch Catalysts: An In Situ Spectroscopic Study

Although ruthenium is a common promoter for cobalt-based Fischer–Tropsch synthesis (FTS) catalysts, the origin of Ru promotion and promoter concentration effects remains controversial. To gain a fundamental understanding of the Ru promotion effects, we herein performed an in situ spectroscopic study by X-ray absorption spectroscopy (XAS), Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS)–Auger of working Co/TiO 2 catalysts (ca. 12 wt % Co, pure anatase TiO2 phase) promoted with different amounts of Ru (0.1–1.2 wt %). At typical FTS conditions (220 °C, 20 bar, H 2 /CO = 2), the activity in terms of both metal-time-yield (MTY) and initial turnover frequency (TOF) was maximized for the catalysts promoted with 0.1–0.2 wt % Ru, for which most of the Ru was alloyed with Co in bimetallic nanoparticles. The analysis of Auger electrons evidenced that the lower (apparent) TOF of accessible Co0 sites in the absence of Ru and at Ru concentrations beyond 0.2 wt % is bridged to the development, under reaction conditions, of FTS-inactive cobalt carbide (CoC x ) and cobalt oxide (CoO x ) patches, respectively, at the outermost surface of cobalt crystallites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spin liquid to spin glass crossover in the random quantum Heisenberg magnet

We study quantum SU($M$) spins with all-to-all and random Heisenberg exchange interactions of root-mean-square strength $J$. The $M \rightarrow \infty$ model has a spin liquid ground state with the spinons obeying the equations of the Sachdev-Ye-Kitaev (SYK) model. Numerical studies of the SU(2) model with $S=1/2$ spins show spin glass order in the ground state, but also display SYK spin liquid behavior in the intermediate frequency spin spectrum. We employ a $1/M$ expansion to describe the crossover from fractionalized fermionic spinons to a confining spin glass state with weak spin glass order $q_{EA}$. The SYK spin liquid behavior persists down to a frequency $\omega_\ast \sim J q_{EA}$, and for $\omega < \omega_\ast$, the spectral density is linear in $\omega$, thus quenching the extensive zero temperature entropy of the spin liquid. Furthermore, the linear $\omega$ spectrum is qualitatively similar to that obtained earlier using bosonic spinons for large $q_{EA}$. We argue that the extensive SYK spin liquid entropy is transformed as $T \rightarrow 0$ to an extensive complexity of the spin glass state.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Structural and thermodynamic effects of hydration in Na-zeolite A (LTA) from low-temperature heat capacity

Zeolite A (Linde Type A; LTA) is an industrially important porous mineral that has recently been shown to exhibit framework flexibility upon changes in hydration level. Here, to investigate the flexibility transition from a thermodynamic perspective, we have performed heat capacity measurements on sodium zeolite A at seven incremental hydration levels ranging from zero to equilibrium with ambient air. Excess low-frequency vibrations beyond the predictions of the Debye model are found in all samples, and the frequency of these vibrations increases as a function of hydration level. This suggests that an increase in hydration causes a decrease in at least one type of framework flexibility for sodium zeolite A. In addition, a subtle excess heat capacity contribution from 150 to 280 K is observed only for low and intermediate hydration levels, which may arise from a transformation tied to framework flexibility previously observed in zeolite A via gas absorption calorimetry. Values of the standard thermodynamic functions C p,m °, Δ 0 T S m °, Δ 0 T H m °, and Φ m ° are also reported.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗