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Microkinetic Modeling: A Tool for Rational Catalyst Design

The design of heterogeneous catalysts relies on understanding the fundamental surface kinetics that controls catalyst performance, and microkinetic modeling is a tool that can help the researcher in streamlining the process of catalyst design. Microkinetic modeling is used to identify critical reaction intermediates and rate-determining elementary reactions, thereby providing vital information for designing an improved catalyst. In this review, we summarize general procedures for developing microkinetic models using reaction kinetics parameters obtained from experimental data, theoretical correlations, and quantum chemical calculations. We examine the methods required to ensure the thermodynamic consistency of the microkinetic model. We describe procedures required for parameter adjustments to account for the heterogeneity of the catalyst and the inherent errors in parameter estimation. We discuss the analysis of microkinetic models to determine the rate determining reactions using the degree of rate control and reversibility of each elementary reaction. We introduce incorporation of Brønsted–Evans–Polanyi relations and scaling relations in microkinetic models and the effects of these relations on catalytic performance and formation of volcano curves. We review the analysis of reaction schemes in terms of the maximum rate of elementary reactions, and we outline a procedure to identify kinetically significant transition states and adsorbed intermediates. Here, we explore the application of generalized rate expressions for the prediction of optimal binding energies of important surface intermediates and to estimate the extent of potential rate improvement. We also explore the application of microkinetic modeling in homogeneous catalysis, electro-catalysis, and transient reaction kinetics. We conclude by highlighting the challenges and opportunities in the application of microkinetic modeling for catalyst design.

42 ENGINEERING↗

Challenges in Coupling Acidity and Salinity Transport in Porous Media

Salinity is an increasingly prescient issue in reactive transport, from low salinity water flooding to fracking brine leakage. Of primary concern is the effect of salinity on surface chemistry. Transport and batch experiments show a strong coupling of salinity and acidity through chemical interactions at the mineral–liquid interface. This coupling is ascribed to the combined effects of ionic strength on electrostatic behavior of the interface and competitive sorption between protons and other cations for binding sites on the surface. The effect of these mechanisms is well studied in batch settings and readily describes observed behavior. In contrast, the transport literature is sparse, primarily applied to synthetic materials, and offers only qualitative agreement with observations. To address, this gap in knowledge, we conduct a suite of column flood experiments through silica sand, systematically varying salinity and acidity conditions. Experiments are compared to a reactive transport model incorporating the proposed coupling mechanisms. The results highlight the difficulty in applying such models to realistic media under both basic and acidic conditions with a single set of parameters. The analysis and experimental results show the observed error is the result of electrostatic assumptions within the surface chemistry model and provide a strong constraint on further model development.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DFT Accurate Interatomic Potential for Molten NaCl from Machine Learning

Molten alkali chloride salts are a critical component in concentrated solar power and nuclear applications. Despite their ubiquity, the extreme chemical reactivity of molten alkali chlorides at high temperatures has presented a significant challenge in characterizing atomic structures and dynamic properties experimentally. In this work, we we investigate molten NaCl by performing high temperature molecular dynamics simulations using a Gaussian Approximation Potential (GAP) trained on Density Functional Theory (DFT) datasets. Our GAP model, trained with a meager 1000 atomic configurations, arrives at near ab initio accuracy with a mean absolute error of 1.5 meV/atom thus enabling fast analysis of high temperature salt properties on large length (5000 ion pairs) and time (> 1ns) scales currently inaccessible to ab initio simulations. Calculated structure factors and diffusion constants from our GAP model simulations show excellent agreement with experiments. Our results indicate that GAP models are able to capture the many-body interactions required to accurately model ionic-systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On the Role of Macrophysics and Microphysics in Km-Scale Simulations of Mixed-Phase Clouds During Cold Air Outbreaks

Regional atmospheric models struggle to maintain supercooled liquid in mixed-phase clouds during polar cold-air outbreaks (CAOs). Previous studies focused on the parameterization of aerosol, microphysics and turbulence to understand the origin of this widespread model bias. This study investigates the role of sub-grid cloud fraction parameterizations (CFP) in the simulation of mixed-phase cloud. Km-scale simulations are performed for a large number of CAO cases over Norway, for which continuous ground observations were collected at one site over 6 months. We use a novel analysis that attributes the cloud-radiative errors to deficiencies in specific cloud regimes. We show that the CFP matters for cloud-radiative effects in CAOs, but that it is probably not the primary cause of the lack of liquid water in simulated mixed-phase clouds. Of all the CFP sensitivities explored in this study, the prognostic representation of both liquid and ice shows most promise in increasing the liquid water path. A newly proposed hybrid CFP with prognostic frozen and diagnostic liquid cloud fraction reproduces some of the benefits of the prognostic scheme at reduced cost and complexity. All simulations appear to produce too large precipitation particles. As a result, reducing the snow deposition rate increases the liquid water path and improves the precipitation size distributions, while simulations are less sensitive to reduced riming rates.

54 ENVIRONMENTAL SCIENCES↗

Baryon acoustic oscillations from the complete SDSS-III Lyα-quasar cross-correlation function at z = 2.4

We present a measurement of baryon acoustic oscillations (BAO) in the cross-correlation of quasars with the Lyα-forest flux-transmission at a mean redshift z = 2.40. The measurement uses the complete SDSS-III data sample: 168,889 forests and 234,367 quasars from the SDSS Data Release DR12. In addition to the statistical improvement on our previous study using DR11, we have implemented numerous improvements at the analysis level allowing a more accurate measurement of this cross-correlation. We also developed the first simulations of the cross-correlation allowing us to test different aspects of our data analysis and to search for potential systematic errors in the determination of the BAO peak position. We measure the two ratios D H (z = 2.40)=r d = 9.01 ± 0.36 and D M (z = 2.40)=r d = 35.7 ±1.7, where the errors include marginalization over the non-linear velocity of quasars and the metal - quasar cross-correlation contribution, among other effects. These results are within 1.8σ of the prediction of the flat-ΛCDM model describing the observed CMB anisotropies.We combine this study with the Lyα-forest auto-correlation function (Bautista et al. 2017), yielding D H (z = 2.40)=r d = 8.94 ± 0.22 and D M (z = 2.40)=r d = 36.6 ± 1.2, within 2.3σ of the same flat-ΛCDM model.

79 ASTRONOMY AND ASTROPHYSICS↗

Experimental limits on primordial black hole dark matter from the first 2 yr of Kepler data

We present our analysis on new limits of the dark matter (DM) halo consisting of primordial black holes (PBHs) or massive compact halo objects. We present a search of the first two yr of publicly available Kepler mission data for potential signatures of gravitational microlensing caused by these objects as well as an extensive analysis of the astrophysical sources of background error. These include variable stars, flare events, and comets or asteroids that are moving through the Kepler field. We discuss the potential of detecting comets using the Kepler light curves, presenting measurements of two known comets and one unidentified object, most likely an asteroid or comet. After removing the background events with statistical cuts, we find no microlensing candidates. We therefore present our Monte Carlo efficiency calculation in order to constrain the PBH DM with masses in the range of 2 × 10{sup –9} M {sub ☉} to 10{sup –7} M {sub ☉}. We find that PBHs in this mass range cannot make up the entirety of the DM, thus closing a full order of magnitude in the allowed mass range for PBH DM.

79 ASTRONOMY AND ASTROPHYSICS↗

IMPROVED Ti II log(gf) VALUES AND ABUNDANCE DETERMINATIONS IN THE PHOTOSPHERES OF THE SUN AND METAL-POOR STAR HD 84937

Atomic transition probability measurements for 364 lines of Ti II in the UV through near-IR are reported. Branching fractions from data recorded using a Fourier transform spectrometer (FTS) and a new echelle spectrometer are combined with published radiative lifetimes to determine these transition probabilities. The new results are in generally good agreement with previously reported FTS measurements. Use of the new echelle spectrometer, independent radiometric calibration methods, and independent data analysis routines enables a reduction of systematic errors and overall improvement in transition probability accuracy over previous measurements. The new Ti II data are applied to high-resolution visible and UV spectra of the Sun and metal-poor star HD 84937 to derive new, more accurate Ti abundances. Lines covering a range of wavelength and excitation potential are used to search for non-LTE effects. The Ti abundances derived using Ti II for these two stars match those derived using Ti I and support the relative Ti/Fe abundance ratio versus metallicity seen in previous studies.

79 ASTRONOMY AND ASTROPHYSICS↗

Efficacy of the Method of Four Coefficients to Determine Charge-Carrier Scattering

The investigation of the electronic properties of semiconductors from transport measurements (i.e., resistivity, Hall, and Seebeck coefficient measurements) is challenging due to the averaging of charge-carrier dynamics inherent in such measurements. Here, we investigate the incorporation of a fourth measurement of electronic transport, the Nernst coefficient, into the analysis, termed the method of four coefficients. This approach yields the Fermi level, effective mass, scattering exponent, and relaxation time prefactor. We begin with a review of the underlying mathematics and investigate the mapping between the four-dimensional material property and transport coefficient spaces. We then investigate how the traditional single-parabolic band method yields a single, potentially incorrect point on the solution subspace. This uncertainty can be resolved through Nernst coefficient measurements and we map the span of the ensuing subspace. We conclude with an investigation of how sensitive the analysis of transport coefficients is to experimental error for different sample types.

charge carriers↗

Model independent comparison of supernova and strong lensing cosmography: Implications for the Hubble constant tension

We use supernovae measurements, calibrated by the local determination of the Hubble constant $H_0$ by SH0ES, to interpolate the distance-redshift relation using Gaussian process regression. We then predict, independent of the cosmological model, the distances that are measured with strong lensing time delays to test their mutual agreement. In this work we find excellent agreement between these predictions and the measurements. The agreement holds when we consider only the redshift dependence of the distance-redshift relation, independent of the value of $H_0$. Our results disfavor the possibility that lens mass modeling contributes a 10% bias or uncertainty in the strong lensing analysis, as suggested recently in the literature. In general our analysis strengthens the case that residual systematic errors in both measurements are below the level of the current discrepancy with the CMB determination of $H_0$, and supports the possibility of new physical phenomena on cosmological scales. With additional data our methodology can provide more stringent tests of unaccounted for systematics in the determinations of the distance-redshift relation in the late universe.

79 ASTRONOMY AND ASTROPHYSICS↗

Precise cosmological constraints from BOSS galaxy clustering with a simulation-based emulator of the wavelet scattering transform

For this study, we perform a reanalysis of the BOSS CMASS DR12 galaxy dataset using a simulation-based emulator for the wavelet scattering transform (WST) coefficients. Moving beyond our previous works, which laid the foundation for the first galaxy clustering application of this estimator, we construct a neural net-based emulator for the cosmological dependence of the WST coefficients and the 2-point correlation function multipoles, trained from the state-of-the-art suite of abacussummit simulations combined with a flexible halo occupation distribution (HOD) galaxy model. In order to confirm the accuracy of our pipeline, we subject it to a series of thorough internal and external mock parameter recovery tests, before applying it to reanalyze the CMASS observations in the redshift range 0.46 < z < 0.57. We find that a joint WST+2-point correlation function likelihood analysis allows us to obtain marginalized 1⁢σ errors on the Λ⁢ CDM parameters that are tighter by a factor of 2.5–6, compared to the 2-point correlation function, and by a factor of 1.4–2.5 compared to the WST-only results. This corresponds to a competitive 0.9%, 2.3% and 1% level of determination for parameters ω c , ⁢σ 8 &n s , respectively, and also to a 0.7% and 2.5% constraint on derived parameters h and ƒ⁡(z)⁢⁢σ 8 ⁡(z), in agreement with the Planck 2018 results. Our results reaffirm the constraining power of the WST and highlight the exciting prospect of employing higher-order statistics in order to fully exploit the power of upcoming stage-IV spectroscopic observations.

79 ASTRONOMY AND ASTROPHYSICS↗

Introductory guide to backgrounds in XPS spectra and their impact on determining peak intensities

Photoelectron and Auger peaks are central to most of the important uses of x-ray photoelectron spectroscopy (XPS), and thus, they receive the most attention in many types of analysis. Quantitative chemical analysis using XPS requires the assessment of the intensities of the photoemission peaks of the elements detected. Determination of peak intensities requires separation of the photoelectron peak signals from the background on which the peaks rest. For the determination of peak area intensities, the background is subtracted from overall signal intensity. The spectral background is also critical when peak fitting is used to determine intensities of overlapping peaks, and the model of background used in this process can impact the results. In addition to the impact on quantitative analysis, information about the depth distribution of elements in the near surface region can often be obtained by visual inspection of the background and quantified using appropriate modeling. Here, this introductory guide provides some basic information about backgrounds in the XPS analysis, describes the types of background models that are commonly used, suggests some of their strengths and weaknesses, and provides examples of their use and misuse. Although the fundamental nature of some components of the background signals in XPS is not understood, indicating that none of the models in use are fully correct and the area is subject to active research, appropriate good practices have been established for most routine analysis. The guide describes good practices, identifies errors that frequently appear in the literature, and uses examples to demonstrate the impacts of background selections on determinations of peak intensities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

SU-E-T-144: Effective Analysis of VMAT QA Generated Trajectory Log Files for Medical Accelerator Predictive Maintenance

Purpose: To determine the effectiveness of SPC analysis for a model predictive maintenance process that uses accelerator generated parameter and performance data contained in trajectory log files. Methods: Each trajectory file is decoded and a total of 131 axes positions are recorded (collimator jaw position, gantry angle, each MLC, etc.). This raw data is processed and either axis positions are extracted at critical points during the delivery or positional change over time is used to determine axis velocity. The focus of our analysis is the accuracy, reproducibility and fidelity of each axis. A reference positional trace of the gantry and each MLC is used as a motion baseline for cross correlation (CC) analysis. A total of 494 parameters (482 MLC related) were analyzed using Individual and Moving Range (I/MR) charts. The chart limits were calculated using a hybrid technique that included the use of the standard 3σ limits and parameter/system specifications. Synthetic errors/changes were introduced to determine the initial effectiveness of I/MR charts in detecting relevant changes in operating parameters. The magnitude of the synthetic errors/changes was based on: TG-142 and published analysis of VMAT delivery accuracy. Results: All errors introduced were detected. Synthetic positional errors of 2mm for collimator jaw and MLC carriage exceeded the chart limits. Gantry speed and each MLC speed are analyzed at two different points in the delivery. Simulated Gantry speed error (0.2 deg/sec) and MLC speed error (0.1 cm/sec) exceeded the speed chart limits. Gantry position error of 0.2 deg was detected by the CC maximum value charts. The MLC position error of 0.1 cm was detected by the CC maximum value location charts for every MLC. Conclusion: SPC I/MR evaluation of trajectory log file parameters may be effective in providing an early warning of performance degradation or component failure for medical accelerator systems.

61 RADIATION PROTECTION AND DOSIMETRY↗

SU-E-T-492: Implementing a Method for Brain Irradiation in Rats Utilizing a Commercially Available Radiosurgery Irradiator

Purpose: The purpose of the study was to implement a method for accurate rat brain irradiation using the Gamma Knife Perfexion unit. The system needed to be repeatable, efficient, and dosimetrically and spatially accurate. Methods: A platform (“rat holder”) was made such that it is attachable to the Leskell Gamma Knife G Frame. The rat holder utilizes two ear bars contacting bony anatomy and a front tooth bar to secure the rat. The rat holder fits inside of the Leskell localizer box, which utilizes fiducial markers to register with the GammaPlan planning system. This method allows for accurate, repeatable setup.A cylindrical phantom was made so that film can be placed axially in the phantom. We then acquired CT image sets of the rat holder and localizer box with both a rat and the phantom. Three treatment plans were created: a plan on the rat CT dataset, a phantom plan with the same prescription dose as the rat plan, and a phantom plan with the same delivery time as the rat plan. Results: Film analysis from the phantom showed that our setup is spatially accurate and repeatable. It is also dosimetrically accurate, with an difference between predicted and measured dose of 2.9%. Film analysis with prescription dose equal between rat and phantom plans showed a difference of 3.8%, showing that our phantom is a good representation of the rat for dosimetry purposes, allowing for +/- 3mm diameter variation. Film analysis with treatment time equal showed an error of 2.6%, which means we can deliver a prescription dose within 3% accuracy. Conclusion: Our method for irradiation of rat brain has been shown to be repeatable, efficient, and accurate, both dosimetrically and spatially. We can treat a large number of rats efficiently while delivering prescription doses within 3% at millimeter level accuracy.

60 APPLIED LIFE SCIENCES↗

MO-G-18C-03: Evaluation of Deformable Image Registration for Lung Motion Estimation Using Hyperpolarized Gas Tagging MRI

Purpose: Hyperpolarized gas (HP) tagging MRI is a novel imaging technique for direct measurement of lung motion during breathing. This study aims to quantitatively evaluate the accuracy of deformable image registration (DIR) in lung motion estimation using HP tagging MRI as references. Methods: Three healthy subjects were imaged using the HP MR tagging, as well as a high-resolution 3D proton MR sequence (TrueFISP) at the end-of-inhalation (EOI) and the end-of-exhalation (EOE). Ground truth of lung motion and corresponding displacement vector field (tDVF) was derived from HP tagging MRI by manually tracking the displacement of tagging grids between EOI and EOE. Seven different DIR methods were applied to the high-resolution TrueFISP MR images (EOI and EOE) to generate the DIR-based DVFs (dDVF). The DIR methods include Velocity (VEL), MIM, Mirada, multi-grid B-spline from Elastix (MGB) and 3 other algorithms from DIRART toolbox (Double Force Demons (DFD), Improved Lucas-Kanade (ILK), and Iterative Optical Flow (IOF)). All registrations were performed by independent experts. Target registration error (TRE) was calculated as tDVF – dDVF. Analysis was performed for the entire lungs, and separately for the upper and lower lungs. Results: Significant differences between tDVF and dDVF were observed. Besides the DFD and IOF algorithms, all other dDVFs showed similarity in deformation magnitude distribution but away from the ground truth. The average TRE for entire lung ranged 2.5−23.7mm (mean=8.8mm), depending on the DIR method and subject's breathing amplitude. Larger TRE (13.3–23.7mm) was found in subject with larger breathing amplitude of 45.6mm. TRE was greater in lower lung (2.5−33.9 mm, mean=12.4mm) than that in upper lung (2.5−11.9 mm, mean=5.8mm). Conclusion: Significant differences were observed in lung motion estimation between the HP gas tagging MRI method and the DIR methods, especially when lung motion is large. Large variation among different DIR methods was also observed.

60 APPLIED LIFE SCIENCES↗

Process-based quality management for clinical implementation of adaptive radiotherapy

Purpose: Intensity-modulated adaptive radiotherapy (ART) has been the focus of considerable research and developmental work due to its potential therapeutic benefits. However, in light of its unique quality assurance (QA) challenges, no one has described a robust framework for its clinical implementation. In fact, recent position papers by ASTRO and AAPM have firmly endorsed pretreatment patient-specific IMRT QA, which limits the feasibility of online ART. The authors aim to address these obstacles by applying failure mode and effects analysis (FMEA) to identify high-priority errors and appropriate risk-mitigation strategies for clinical implementation of intensity-modulated ART. Methods: An experienced team of two clinical medical physicists, one clinical engineer, and one radiation oncologist was assembled to perform a standard FMEA for intensity-modulated ART. A set of 216 potential radiotherapy failures composed by the forthcoming AAPM task group 100 (TG-100) was used as the basis. Of the 216 failures, 127 were identified as most relevant to an ART scheme. Using the associated TG-100 FMEA values as a baseline, the team considered how the likeliness of occurrence (O), outcome severity (S), and likeliness of failure being undetected (D) would change for ART. New risk priority numbers (RPN) were calculated. Failures characterized by RPN ≥ 200 were identified as potentially critical. Results: FMEA revealed that ART RPN increased for 38% (n = 48/127) of potential failures, with 75% (n = 36/48) attributed to failures in the segmentation and treatment planning processes. Forty-three of 127 failures were identified as potentially critical. Risk-mitigation strategies include implementing a suite of quality control and decision support software, specialty QA software/hardware tools, and an increase in specially trained personnel. Conclusions: Results of the FMEA-based risk assessment demonstrate that intensity-modulated ART introduces different (but not necessarily more) risks than standard IMRT and may be safely implemented with the proper mitigations.

60 APPLIED LIFE SCIENCES↗

SU-F-T-207: Does the Greater Flexibility of Pencil Beam Scanning Reduce the Need for a Proton Gantry?

Purpose: Gantry-less proton treatment facility could lower the capital cost of proton therapy. This study investigates the dosimetric feasibility of using only coplanar pencil beam scanning (PBS) beams for those patients who had beam angles that would not have been deliverable without the gantry. Those coplanar beams are implemented on gantry-less horizontal beam-line with patients in sitting or standing positions. Methods: We have selected ten patients (seven head-and-neck, one thoracic, one abdominal and one pelvic case) with clinically delivered double scattering (DS) or PBS treatment plans with beam angles that were challenging to achieve without a gantry. After removing these beams angles, PBS plans were optimized for gantry-less intensity modulated proton therapy (IMPT) or single field optimization (SFO) with multi-criteria optimization (MCO). For head-and-neck patients who were treated by DS, we generated PBS plans with non-coplanar beams for comparison. Dose-volume-histograms (DVHs), target homogeneity index (HI), mean dose, D-2 and D-98 were reported. Robustness analysis was performed with ±2.5 mm setup errors and ±3.5% range uncertainties for three head-and-neck patients. Results: PBS-gantry-less plans provided more homogenous target coverage and significant improvements on organs-at-risk (OARs) sparing, compared to passive scattering treatments with a gantry. The PBS gantry-less treatments reduced the HI for target coverage by 1.3% to 47.2%, except for a suprasellar patient and a liver patient. The PBS-gantry-less plans reduced the D-mean of OARs by 3.6% to 67.4%. The PBS-gantry plans had similar target coverage and only marginal improvements on OAR sparing as compared to the PBS-gantry-less plans. These two PBS plans also had similar robustness relative to range uncertainties and setup errors. Conclusion: The gantry-less plans have with less mean dose to OARs and more homogeneous target coverage. Although the PBS-gantry plans have slightly improved target coverage and OARs sparing, the overall benefit of having a gantry to provide non-coplanar beams is debatable.

60 APPLIED LIFE SCIENCES↗

bnl/pub-Maffettone_2020_08

The application of the XCA package as first demonstrated in aXiv:2008.00283. ABSTRACT: The discovery of new structural and functional materials is driven by phase identification, often using X-ray diffraction (XRD). Automation has accelerated the rate of XRD measurements, greatly outpacing XRD analysis techniques that remain manual, time consuming, error prone, and impossible to scale. With the advent of autonomous robotic scientists or self-driving labs, contemporary techniques prohibit the integration of XRD. Here, we describe a computer program for the autonomous characterization of XRD data, driven by artificial intelligence (AI), for the discovery of new materials. Starting from structural databases, we train an ensemble model using a physically accurate synthetic dataset, which output probabilistic classifications --- rather than absolutes --- to overcome the overconfidence in traditional neural networks. This AI agent behaves as a companion to the researcher, improving accuracy and offering unprecedented time savings, and is demonstrated on a diverse set of organic and inorganic materials challenges. This innovation is directly applicable to inverse design approaches, robotic discovery systems, and can be immediately considered for other forms of characterization such as spectroscopy and the pair distribution function.

Maffettone, PhillipM [Brookhaven National Lab. (BN↗

ADEPT, a dynamic next generation sequencing data error-detection program with trimming

Illumina is the most widely used next generation sequencing technology and produces millions of short reads that contain errors. These sequencing errors constitute a major problem in applications such as de novo genome assembly, metagenomics analysis and single nucleotide polymorphism discovery. In this study, we present ADEPT, a dynamic error detection method, based on the quality scores of each nucleotide and its neighboring nucleotides, together with their positions within the read and compares this to the position-specific quality score distribution of all bases within the sequencing run. This method greatly improves upon other available methods in terms of the true positive rate of error discovery without affecting the false positive rate, particularly within the middle of reads. We conclude that ADEPT is the only tool to date that dynamically assesses errors within reads by comparing position-specific and neighboring base quality scores with the distribution of quality scores for the dataset being analyzed. The result is a method that is less prone to position-dependent under-prediction, which is one of the most prominent issues in error prediction. The outcome is that ADEPT improves upon prior efforts in identifying true errors, primarily within the middle of reads, while reducing the false positive rate.

59 BASIC BIOLOGICAL SCIENCES↗