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At least 325 records · Page 18

Cryo-electron tomography related radiation-damage parameters for individual-molecule 3D structure determination

To understand the dynamic structure–function relationship of soft- and biomolecules, the determination of the three-dimensional (3D) structure of each individual molecule (nonaveraged structure) in its native state is sought-after. Cryo-electron tomography (cryo-ET) is a unique tool for imaging an individual object from a series of tilted views. However, due to radiation damage from the incident electron beam, the tolerable electron dose limits image contrast and the signal-to-noise ratio (SNR) of the data, preventing the 3D structure determination of individual molecules, especially at high-resolution. Although recently developed technologies and techniques, such as the direct electron detector, phase plate, and computational algorithms, can partially improve image contrast/SNR at the same electron dose, the high-resolution structure, such as tertiary structure of individual molecules, has not yet been resolved. Here, we review the cryo-electron microscopy (cryo-EM) and cryo-ET experimental parameters to discuss how these parameters affect the extent of radiation damage. This discussion can guide us in optimizing the experimental strategy to increase the imaging dose or improve image SNR without increasing the radiation damage. With a higher dose, a higher image contrast/SNR can be achieved, which is crucial for individual-molecule 3D structure. With 3D structures determined from an ensemble of individual molecules in different conformations, the molecular mechanism through their biochemical reactions, such as self-folding or synthesis, can be elucidated in a straightforward manner.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

HydraGNN_Predictive_GFM_2024 - Ensemble of predictive graph foundation models for ground state atomistic materials modeling

We provide the ensemble of fifteen pre-trained graph foundation models (GFMs) for atomistic materials modeling applications. Each one of the fifteen GFMs has been trained on five open-source datasets that (once aggregated) amount to over 154 million atomistic structures, which cover over two-thirds of the natural elements of the periodic table and that comprises a broad set of organic and inorganic compounds. This vast set of atomistic structures comprises ground state configurations that are dynamically stable (i.e., equilibrated structures with atomic forces approximately close to zero values) as well as dynamically unstable structures (i.e., non-equilibrium structures with non-negligible non-zero values of atomic forces). The ensemble of datasets aggregated does NOT include excited states. The datasets have been curated to remove atomistic structures with spectral norm of the force tensor above 100 eV/angstrom. Moreover, a linear term of the energy was computed for each dataset using a linear regression model that uses the chemical concentration of each natural element as regressor. The linear term predicted by the linear regression model has been subtracted from each original energy value to perform a re-alignment of the energy values across different electronic structures approximation theories performed to generate the diverse multi-source, multi-fidelity datasets. The folder "ADIOS_files" contains the set of pre-processed datasets in Adaptable I/O System (ADIOS) format (https://www.exascaleproject.org/research-project/adios/) that have been used for the development and training of GFMs in this work. The "ADIOS_files" directory contains 6 sub-directories named as follows: - ANI1x-v3.bp - MPTrj-v3.bp - OC2020-20M-v3.bp - OC2020-v3.bp - OC2022-v3.bp - qm7x-v3.bp Each sub-directory contains the pre-processed datasets converted in Adaptable I/O System (ADIOS) format (https://www.exascaleproject.org/research-project/adios/) that have been used to the development, training, and performance testing of the ensemble go predictive graph foundation models. Each GFM was developed using HydraGNN (https://github.com/ORNL/HydraGNN) as underlying graph neural network (GNN) architecture. The multi-task learning (MTL) capability of HydraGNN was used to simultaneously train the GFMs on labeled values for direct predictions of energy (a total system property of an atomistic structure that measures the chemical stability) and atomic forces (an atomic level property of an atomistic structure that measures the dynamical stability). The hyper parameters of the GFM have been tuned using scalable hyperparameter optimization (HPO) algorithms implemented in the software DeepHyper (https://github.com/deephyper/deephyper). The pre-training of each HPO trial was performed using distributed data parallelism (DDP) to scale the training across 128 compute nodes of the exascale OLCF supercomputer Frontier. Each HPO trial was trained only for 10 epochs and an early stopping was performed to avoid wasting significant computational resources on GNN architectures that were clearly underperforming. For each HPO trial, the 'omnistat' tool developed by (AMD Research - Advanced Micro Device) was used to measure the total energy consumption in kWh. The ensemble of GFMs was obtained by selecting the fifteen best performing HPO trials. Four models have been selected for their clear advantage in accuracy, and these are the GFMs with IDs 229, 156, 147, 260. Additional eleven models have been selected based on judicious balance between accuracy and energy consumption needed for training, and these are the GFMs with IDs 165, 78, 137, 1, 175, 171, 181, 67, 179, 167, 351. Each selected GFM of the ensemble was continued to cumulate a total of at most 30 epochs. In some cases, the total number of epochs actually performed was les than 30 due to two combined factors: (1) the size of the GFM (i.e., the number of model parameters to train) and (2) the total wall-clock time for which the computational resources could be allocated on OLCF-Frontier. The "Ensemble_of_models" directory contains 15 sub-directories named as follows: - gfm_0.229 - gfm_0.156 - gfm_0.147 - gfm_0.260 - gfm_0.165 - gfm_0.78 - gfm_0.137 - gfm_0.1 - gfm_0.175 - gfm_0.171 - gfm_0.181 - gfm_0.67 - gfm_0.179 - gfm_0.167 - gfm_0.351 Each one of these sub-directories refers to one of the fifteen HPO trials that have been selected to continue the pre-training with at most 30 epochs. With each sub-directory associated with a specific HPO trial, the following files can be found: - config.json: file for argument parsing to develop and train an HydraGNN architecture - gfm_0.ID_epoch_N.pk: file with model parameters for HPO ID trial after N epochs of training The ensemble of fifteen GFM architectures was used for (1) ensemble averaging to stabilize the predictions of energy and atomic forces after pre-training for post-processing analysis and (2) ensemble uncertainty quantification (UQ). The code used to develop, pre-train, and load the pre-trained models for post-processing analysis is available on the ORNL-GitHub at the following link: https://github.com/ORNL/HydraGNN/tree/Predictive_GFM_2024

36 MATERIALS SCIENCE↗

Quantal diffusion approach for multinucleon transfer processes in the 58,64 Ni + 208 Pb reactions: Toward the production of unknown neutron-rich nuclei

In recent years, substantial efforts have been made for the study of multinucleon transfer reactions at energies around the Coulomb barrier both experimentally and theoretically, aiming at the production of unknown neutron-rich heavy nuclei. It is crucial to provide reliable theoretical predictions based on microscopic theories with sufficient predictive power. Purpose: This article aims to clarify the applicability of the quantal diffusion approach based on the stochastic mean-field (SMF) theory for multinucleon transfer processes. Isotope production cross sections are evaluated for the reactions of 64 Ni + 208 Pb at E c.m. = 268 MeV and 58 Ni + 208 Pb at E c.m. = 270 MeV and are compared with available experimental data. Methods: Three-dimensional time-dependent Hartree-Fock (TDHF) calculations are carried out for a range of initial orbital angular momenta with Skyrme SLy4d functional. Quantal diffusion equations, derived based on the SMF theory, for variances and covariance of neutron and proton numbers of reaction products are solved, with microscopic drift and diffusion coefficients obtained from time evolution of occupied single-particle orbitals in TDHF. Secondary de-excitation processes, both particle evaporation and fission, are simulated by a statistical compound-nucleus de-excitation model, gemini++. Dynamics of a fast isospin equilibration process followed by a slow drift toward the mass symmetry are commonly observed, as expected. Various reaction outcomes are evaluated, including average mass and charge numbers of reaction products, total kinetic energy loss (TKEL), scattering angle, contact time, and production cross sections for primary and secondary products. By comparing with the experimental data, we find that SMF and TDHF quantitatively reproduce experimental data for few-nucleon-transfer channels around the average values. In contrast, for many-nucleon-transfer channels, we find that the SMF approach provides much better description of the experimentally measured isotopic distributions. The results underline the importance of beyond-mean-field effects, especially one-body (mean-field) fluctuations and correlations, in describing multinucleon transfer processes. Moreover, through a combined analysis of SMF with a statistical model, gemini++, we find a significant contribution of transfer-induced fission, which is consistent with the experimental observation. In some cases, the SMF approach overestimates the isotopic width, requiring further improvements of the theoretical description. Possible ways to improve the description are discussed. The SMF approach is designed to describe the quantum many-body problem according to an ensemble of mean-field trajectories, taking into account part of many-body correlations in the description. As it requires feasible computational costs comparable to the ordinary TDHF approach, together with further model improvements, it will be a promising tool in the search for optimal reaction conditions to produce yet-unknown neutron-rich heavy nuclei through the multinucleon transfer reaction.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

The Sparks tracking code

This note introduces a new tracking code, Sparks, built on the foundations laid by hemod4 and designed for fast tracking of large ensembles of single particles over thousands of turns. The code is intended for the rapid evaluation of nonlinear lattice behavior through observables such as detuning, Poincaré sections, and smear, providing a computationally efficient alternative to large-scale dynamic aperture studies during lattice design and optimization.

43 PARTICLE ACCELERATORS↗

STSR-INR: Spatiotemporal super-resolution for multivariate time-varying volumetric data via implicit neural representation

Implicit neural representation (INR) has surfaced as a promising direction for solving different scientific visualization tasks due to its continuous representation and flexible input and output settings. We present STSR-INR, an INR solution for generating simultaneous spatiotemporal super-resolution for multivariate time-varying volumetric data. Inheriting the benefits of the INR-based approach, STSR-INR supports unsupervised learning and permits data upscaling with arbitrary spatial and temporal scale factors. Unlike existing GAN- or INR-based super-resolution methods, STSR-INR focuses on tackling variables or ensembles and enabling joint training across datasets of various spatiotemporal resolutions. Here we achieve this capability via a variable embedding scheme that learns latent vectors for different variables. In conjunction with a modulated structure in the network design, we employ a variational auto-decoder to optimize the learnable latent vectors to enable latent-space interpolation. To combat the slow training of INR, we leverage a multi-head strategy to improve training and inference speed with significant speedup. We demonstrate the effectiveness of STSR-INR with multiple scalar field datasets and compare it with conventional tricubic+linear interpolation and state-of-the-art deep-learning-based solutions (STNet and CoordNet).

97 MATHEMATICS AND COMPUTING↗

Underlying Fundamentals of Kalman Filtering for River Network Modeling

The grand challenge of producing hydrometeorological estimates every time and everywhere has motivated the fusion of sparse observations with dense numerical models, with a particular interest on discharge in river modeling. Ensemble methods are largely preferred as they enable the estimation of error properties, but at the expense of computational load and generally with underestimations. These imperfect stochastic estimates motivate the use of correction methods, that is, error localization and inflation, although the physical justifications for their optimality are limited. The purpose of this study is to use one of the simplest forms of data assimilation when applied to river modeling and reveal the underlying mechanisms impacting its performance. Our framework based on assimilating daily averaged in situ discharge measurements to correct daily averaged runoff was tested over a 4-yr case study of two rivers in Texas. Results show that under optimal conditions of inflation and localization, discharge simulations are consistently improved such that the mean values of Nash–Sutcliffe efficiency are enhanced from211.32 to 0.55 at observed gauges and from212.24 to21.10 at validation gauges. Yet, parameters controlling the inflation and the localization have a large impact on the performance. Further investigations of these sensitivities showed that optimal inflation occurs when compensating exactly for discrepancies in the magnitude of errors while optimal localization matches the distance traveled during one assimilation window. These results may be applicable to more advanced data assimilation methods as well as for larger applications motivated by upcoming river-observing satellite missions, such as NASA’s Surface Water and Ocean Topography mission.

Streamflow↗

Starting Vortex Identified as Key to Unsteady Ejector Performance

Unsteady ejectors are currently under investigation for use in some pulse-detonation-engine-based propulsion systems. Experimental measurements made in the past, and recently at the NASA Glenn Research Center, have demonstrated that thrust augmentation can be enhanced considerably when the driver is unsteady. In ejector systems, thrust augmentation is defined as = T(sup Total)/T(sup j), where T(sup Total) is the total thrust of the combined ejector and driving jet and T(sup j) is the thrust due to the driving jet alone. There are three images in this figure, one for each of the named thrust sources. The images are color contours of measured instantaneous vorticity. Each image is an ensemble average of at least 150 phase-locked measurements. The flow is from right to left, and the shape and location of each driver is shown on the far right of each image. The emitted vortex is a clearly defined "doughnut" of highly vortical (spinning) flow. In these planar images, the vortex appears as two distorted circles, one above, and one below the axis of symmetry. Because they are spinning in the opposite direction, the two circles have vorticity of opposite sign and thus are different colors. There is also a rectangle shown in each image. Its width represents the ejector diameter that was found experimentally to yield the highest thrust augmentation. It is apparent that the optimal ejector diameter is that which just "captures" the vortex: that is, the diameter bounding the outermost edge of the vortex structure. The exact mechanism behind the enhanced performance is unclear; however, it is believed to be related to the powerful vortex emitted with each pulse of the unsteady driver. As such, particle imaging velocimetry (PIV) measurements were obtained for three unsteady drivers: a pulsejet, a resonance tube, and a speaker-driven jet. All the drivers were tested with ejectors, and all exhibited performance enhancement over similarly sized steady drivers. The characteristic starting vortices of each driver are shown in these images. The images are color contours of measured instantaneous vorticity. Each image is an ensemble average of at least 150 phase-locked measurements. The flow is from right to left. The shape and location of each driver is shown on the far right of each image. The rectangle shown in each image represents the ejector diameter that was found experimentally to yield the highest thrust augmentation. It is apparent that the optimal ejector diameter is that which just "captures" the vortex: that is, the diameter bounding the outermost edge of the vortex structure. Although not shown, it was observed that the emitted vortex spread as it traveled downstream. The spreading rate for the pulsejet is shown as the dashed lines in the top image. A tapered ejector was fabricated that matched this shape. When tested, the ejector demonstrated superior performance to all those previously tested at Glenn (which were essentially of straight, cylindrical form), achieving a remarkable thrust augmentation of 2. The measured thrust augmentation is shown as a function of ejector length. Also shown are the thrust augmentation values achieved with the straight, cylindrical ejectors of varying diameters. Here, thrust augmentation is plotted as a function of ejector length for several families of ejector diameters. It can be seen that large thrust augmentation values are indeed obtained and that they are sensitive to both ejector length and diameter, particularly the latter. Five curves are shown. Four correspond to straight ejector diameters of 2.2, 3.0, 4.0, and 6.0 in. The fifth curve corresponds to the tapered ejector contoured to bound the emitted vortex. For each curve, there are several data points corresponding to different lengths. The largest value of thrust augmentation is 2.0 for the tapered ejector and 1.81 for the straight ejectors. Regardless of their diameters, all the ejectors trend toward peak performance at a particular leng. That the cross-sectional dimensions of optimal ejectors scaled precisely with the vortex dimensions on three separate pulsed thrust sources demonstrates that the action of the vortex is responsible for the enhanced ejector performance. The result also suggests that, in the absence of a complete understanding of the entrainment and augmentation mechanisms, methods of characterizing starting vortices may be useful for correlating and predicting unsteady ejector performance.

Paxson, Daniel E.↗

Profiles of Gamma-Ray Bursts and Their Component Pulses

One physically informative regularity of their otherwise heterogeneous ensemble, is that many Gamma-Ray Bursts consist of well defined pulses. To objectively quantify the temporal structure of BATSE bursts, we have developed an automatic modeling procedure that separates overlapping pulses and determines the energy-dependence of the pulse-shape parameters. No binning of photon arrival times is needed, so when applied to time-tagged events (TTE) the procedure captures variability information down to the shortest time scales present in the raw data. Maximizing the Bayesian likelihood function Pr(data/model) yields estimates of the model parameters, including the number of pulses present, and allows intercomparison of models of different forms. As with any nonlinear optimization, good initial guesses are crucial to avoid convergence to undesirable local minima. We find excellent initial pulse decompositions by wavelet-denoising a cumulative distribution of the raw photon arrival data; differentiation then gives a time profile mostly free of the systematic effects of degraded resolution (as in ordinary Fourier smoothing) and binning. We present statistical information on pulse rise-time, decay-time, peakedness, and amplitudes, plus their energy dependences - both within a single burst and for a large ensemble of bursts.

Scargle, Jeff D.↗

Strong Scalability Analysis of the Albany Land Ice code on HPC Architectures

Scalability is a critical factor in High-Performance Computing (HPC), where optimizing resource usage has a direct impact on cost-effectiveness and time-efficiency. This report presents a strong scaling performance study of the Albany Land Ice (ALI) code across different HPC architectures, towards determining the best configuration to use when running large-scale simulation ensembles.

97 MATHEMATICS AND COMPUTING↗

STITCHES: creating new scenarios of climate model output by stitching together pieces of existing simulations

Abstract. Climate model output emulation has long been attempted to support impact research, mainly to fill in gaps in the scenario space. Given the computational cost of running coupled earth system models (ESMs), which are usually the domain of supercomputers and require on the order of days to weeks to complete a century-long simulation, only a handful of different scenarios are usually chosen to externally force ESM simulations. An effective emulator, able to run on standard computers in times of the order of minutes rather than days could therefore be used to derive climate information under scenarios that were not run by ESMs. Lately, the necessity of accounting for internal variability has also made the availability of initial-condition ensembles, under a specific scenario, important, further increasing the computational demand. At least so far, emulators have been limited to simplified ESM-like output, either seasonal, annual, or decadal averages of basic quantities, like temperature and precipitation, often emulated independently of one another. With this work, we propose a more comprehensive solution to ESM output emulation. Our emulator, STITCHES, uses existing archives of earth system models' (ESMs) scenario experiments to construct ESM-like output under new scenarios or enrich existing initial-condition ensembles, which is what other emulators also aim to do. Importantly, however, STITCHES' output has the same characteristics of the ESM output it sets out to emulate: multivariate, spatially resolved, and high frequency, representing both the forced component and the internal variability around it. STITCHES extends the idea of time sampling – according to which climate outcomes are stratified by the global warming level at which they manifest themselves, irrespective of the scenario and time at which they occur – to the construction of a continuous history of ESM-like output over the whole 21st century, consistent with a 21st-century trajectory of global surface air temperature (GSAT) derived from the scenario that has been chosen as the target of the emulation. STITCHES does so by first splitting the target GSAT trajectory into decade-long windows, then matching each window in turn to a decade-long window within an existing model simulation from the available scenario runs according to its proximity to the target in absolute size of the temperature anomaly and its rate of change. A look-up table is therefore created of a sequence of existing experiment–time-window combinations that, when stitched together, create a GSAT trajectory “similar” to the target. Importantly, we can then stitch together much more than GSAT from these windows, i.e., any output that the ESM has saved for these existing experiment–time-window combinations, at any frequency and spatial scale available in its archive. We show that the stitching does not introduce artifacts in the great majority of cases (we look at temperature and precipitation at monthly frequency and on the native grid of the ESM and at an index of ENSO activity, the Southern Oscillation Index). This is true even if the criteria for the identification of the decades to be stitched together are chosen to work for a smoothed time series of annual GSAT, a result we expect given the larger amount of noise affecting most other variables at finer spatial scales and higher frequencies, which therefore are more “forgiving” of the stitching. We successfully test the method's performance over many ESMs and scenarios. Only a few exceptions surface, but these less-than-optimal outcomes are always associated with a scarcity of the archived simulations from which we can gather the decade-long windows that form the building blocks of the emulated time series. In the great majority of cases, STITCHES' performance is satisfactory according to metrics that reward consistency in trends, interannual and inter-ensemble variance, and autocorrelation structure of the time series stitched together. The method therefore can be used to create ESM-like output according to new scenarios, on the basis of a trajectory of GSAT produced according to that scenario, which could be easily obtained by a simple climate model. It can also be used to increase the size of existing initial-condition ensembles. There are aspects of our emulator that will immediately disqualify it for specific applications, like when climate information is needed whose characteristics result from accumulated quantities over windows of times longer than those used as pieces by STITCHES, droughts longer than a decade for example. But for many applications, we argue that a stitched product can satisfy the climate information needs of impact researchers. STITCHES cannot emulate ESM output from scenarios that result in GSAT trajectories outside of the envelope available in the archive, nor can it emulate trajectories with shapes different from existing ones (overshoots with negative derivative, for example). Therefore, the size and characteristics of the available archives of ESM output are the principal limitations for STITCHES' deployment. Thus, we argue for the possibility of designing scenario experiments within, for example, the next phase of the Coupled Model Intercomparison Project according to new principles, relieved of the need to produce a number of similar trajectories that vary only in radiative forcing strength but more strategically covering the space of temperature anomalies and rates of change.

54 ENVIRONMENTAL SCIENCES↗

CERES: CRISPR Engineering for the Rapid Enhancement of Strains

Previous strain development efforts for cyanobacteria have failed to achieve the necessary productivities needed to support economic biofuel production. We proposed to develop CRISPR Engineering for Rapid Enhancement of Strains (CERES). We developed genetic and computational tools to enable future high-throughput screening of CRISPR interference (CRISPRi) libraries in the cyanobacterium Synechococcus sp. PCC 7002, including: (1) Operon- SEQer: an ensemble of algorithms for predicting operon pairs using RNA-seq data, (2) experimental characterization and machine learning prediction of gRNA design rules for CRISPRi, and (3) a shuttle vector for gene expression. These tools lay the foundation for CRISPR library screening to develop cyanobacterial strains that are optimized for growth or metabolite production under a wide range of environmental conditions. The optimization of cyanobacterial strains will directly advance U.S. energy and climate security by enabling domestic biofuel production while simultaneously mitigating atmospheric greenhouse gases through photoautotrophic fixation of carbon dioxide.

09 BIOMASS FUELS↗

gRASPA

GPU Monte Carlo Simulation Code with a taste of RASPA We present enhancements in Monte Carlo simulation speed and functionality within an open-source code, gRASPA, which uses graphical processing units (GPUs) to achieve significant performance improvements compared to serial, CPU implementations of Monte Carlo. The code supports a wide range of Monte Carlo simulations, including canonical ensemble (NVT), grand canonical, NVT Gibbs, Widom test particle insertions, and continuous-fractional component Monte Carlo. Implementation of grand canonical transition matrix Monte Carlo (GC-TMMC) and a novel feature to allow different moves for the different components of metal-organic framework (MOF) structures exemplify the capabilities of gRASPA for precise free energy calculations and enhanced adsorption studies, respectively. The introduction of a High-Throughput Computing (HTC) mode permits many Monte Carlo simulations on a single GPU device for accelerated materials discovery. The code can incorporate machine learning (ML) potentials. The open-source nature of gRASPA promotes reproducibility and openness in science, and users may add features to the code and optimize it for their own purposes. The code is written in CUDA/C++ and SYCL/C++ to support different GPU vendors. The gRASPA code is publicly available at https://github.com/snurr-group/gRASPA.

Li, Zhao [Purdue/Northwestern/Notre Dame Universit↗

Investigating Particle Size‐Dependent Redox Kinetics and Charge Distribution in Disordered Rocksalt Cathodes

Abstract Understanding how various redox activities evolve and distribute in disordered rocksalt oxides (DRX) can advance insights into manipulating materials properties for achieving stable, high‐energy batteries. Herein, the authors present how the reaction kinetics and spatial distribution of redox activities are governed by the particle size of DRX materials. The size‐dependent electrochemical performance is attributed to the distinct cationic and anionic reaction kinetics at different sizes, which can be tailored to achieve optimal capacity and stability. Overall, the local charged domains in DRX particles display random heterogeneity caused by the isotropic delithiation pathways. Owing to the kinetic limitation, the micron‐sized particles exhibit a holistic “core‐shell” charge distribution, whereas sub‐micron particles show more uniform redox reactions throughout the particles and ensembles. Sub‐micron DRX particles exhibit increasing anionic redox activities yet inferior cycling stability. In summary, engineering particle size can effectively modulate how cationic and anionic redox activities evolve and distribute in DRX materials.

36 MATERIALS SCIENCE↗

Ternary PtIrNi Catalysts for Efficient Electrochemical Ammonia Oxidation

Due to high energy density, carbon-free feature, and easiness to be liquefied, ammonia (NH 3 ) has proved to be an effective alternative to hydrogen in low temperature fuel cells via its direct the ammonia oxidation reaction (AOR) for electricity generation. However, the kinetically sluggish AOR has prohibitively hindered the attractive direct ammonia fuel cell (DAFC) applications. Here we report an efficient AOR catalyst, in which ternary PtIrNi alloy nanoparticles well dispersed on a binary composite support consisting of porous silicon dioxide (SiO 2 ) and carboxyl-functionalized carbon nanotube (PtIrNi/SiO 2 -CNT-COOH) through a sonochemical-assisted synthesis strategy. The PtIrNi alloy nanoparticles, with the aid of abundant OHad provided by porous SiO 2 , and the improved electrical conductivity by CNTs, exhibit remarkable catalytic activity for the AOR in alkaline media. It is evidenced by a lower onset potential (~0.40 V vs. RHE) at room temperature, than that of commercial PtIr/C (ca. 0.43 V vs. RHE). Increasing NH 3 concentrations and operation temperatures significantly improve AOR performance of this catalyst. Specifically, AOR activity of the optimal PtIrNi nanoparticle catalyst can be significantly enhanced by elevating the temperature to 80ºC, with a much lower onset potential (~0.32 V vs. RHE), indicating that DAFC can be operated at higher temperature for increased performance. Constant-potential density functional theory (DFT) calculations showed that the Pt-Ir ensembles on {100}-terminated surfaces serve as the active site. Importantly, the introduction of Ni raises the center energy of the density of states projected onto the group d-orbitals of surface sites and thus lowers the theoretical onset potential for *NH 2 dehydrogenation to *NH when compared to Pt and Pt 3 Ir alloy.

25 ENERGY STORAGE↗

The overlapping fragment approach for non-orthogonal configuration interaction with fragments

The non-orthogonal configuration interaction with fragments (NOCI-F) approach is extended opening the possibility to study intramolecular processes and materials with covalent or ionic lattices. So far, NOCI-F has been applied to study intermolecular energy and electron transfer employing ensembles of fragments that do not have atoms or bonds in common. The here presented approach divides the target system into two overlapping fragments that share one or more atoms and/or one or more bonds. After the construction of a collection of (multiconfigurational) fragment wave functions in a state specific optimization procedure, the fragment wave functions are combined to form many-electron basis functions for the non-orthogonal configuration interaction of the whole system. The orbitals in the overlapping fragment are defined by a corresponding orbital transformation of the fragment orbitals through a singular value decomposition. The overlapping fragments approach is first illustrated for a model system and then used to highlight some possible applications of NOCI with overlapping fragments. In conclusion, the results of excited state diffusion in transition metal oxide, intramolecular singlet fission and magnetic interactions in organic biradicals and ionic compounds are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computational catalyst discovery: Active classification through myopic multiscale sampling

We report the recent boom in computational chemistry has enabled several projects aimed at discovering useful materials or catalysts. We acknowledge and address two recurring issues in the field of computational catalyst discovery. First, calculating macro-scale catalyst properties is not straightforward when using ensembles of atomic-scale calculations [e.g., density functional theory (DFT)]. We attempt to address this issue by creating a multi-scale model that estimates bulk catalyst activity using adsorption energy predictions from both DFT and machine learning models. The second issue is that many catalyst discovery efforts seek to optimize catalyst properties, but optimization is an inherently exploitative objective that is in tension with the explorative nature of early-stage discovery projects. In other words, why invest so much time finding a “best” catalyst when it is likely to fail for some other, unforeseen problem? We address this issue by relaxing the catalyst discovery goal into a classification problem: “What is the set of catalysts that is worth testing experimentally?” Here, we present a catalyst discovery method called myopic multiscale sampling, which combines multiscale modeling with automated selection of DFT calculations. It is an active classification strategy that seeks to classify catalysts as “worth investigating” or “not worth investigating” experimentally. Our results show an ~7–16 times speedup in catalyst classification relative to random sampling. These results were based on offline simulations of our algorithm on two different datasets: a larger, synthesized dataset and a smaller, real dataset.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Using a surrogate-assisted Bayesian framework to calibrate the runoff-generation scheme in the Energy Exascale Earth System Model (E3SM) v1

Abstract. Runoff is a critical component of the terrestrial water cycle, and Earth system models (ESMs) are essential tools to study its spatiotemporal variability. Runoff schemes in ESMs typically include many parameters so that model calibration is necessary to improve the accuracy of simulated runoff. However, runoff calibration at a global scale is challenging because of the high computational cost and the lack of reliable observational datasets. In this study, we calibrated 11 runoff relevant parameters in the Energy Exascale Earth System Model (E3SM) Land Model (ELM) using a surrogate-assisted Bayesian framework. First, the polynomial chaos expansion machinery with Bayesian compressed sensing is used to construct computationally inexpensive surrogate models for ELM-simulated runoff at 0.5∘ × 0.5∘ for 1991–2010. The error metric between the ELM simulations and the benchmark data is selected to construct the surrogates, which facilitates efficient calibration and avoids the more conventional, but challenging, construction of high-dimensional surrogates for the ELM simulated runoff. Second, the Sobol' index sensitivity analysis is performed using the surrogate models to identify the most sensitive parameters, and our results show that, in most regions, ELM-simulated runoff is strongly sensitive to 3 of the 11 uncertain parameters. Third, a Bayesian method is used to infer the optimal values of the most sensitive parameters using an observation-based global runoff dataset as the benchmark. Our results show that model performance is significantly improved with the inferred parameter values. Although the parametric uncertainty of simulated runoff is reduced after the parameter inference, it remains comparable to the multimodel ensemble uncertainty represented by the global hydrological models in ISMIP2a. Additionally, the annual global runoff trend during the simulation period is not well constrained by the inferred parameter values, suggesting the importance of including parametric uncertainty in future runoff projections.

58 GEOSCIENCES↗

An Extensible Perturbed Parameter Ensemble for the Community Atmosphere Model Version 6

This paper documents the methodology and preliminary results from a Perturbed Parameter Ensemble (PPE) technique, where multiple parameters are varied simultaneously and the parameter values are determined with Latin hypercube sampling. This is done with the Community Atmosphere Model version 6 (CAM6), the atmospheric component of the Community Earth System Model version 2 (CESM2). We apply the PPE method to CESM2-CAM6 to understand climate sensitivity to atmospheric physics parameters. The initial simulations vary 45 parameters in the microphysics, convection, turbulence and aerosol schemes with 263 ensemble members. These atmospheric parameters are typically the most uncertain in many climate models. Control simulations are analyzed and targeted simulations to understand climate forcing due to aerosols and fast climate feedbacks. The use of various emulators is explored in the multi- dimensional space mapping input parameters to output metrics. Parameter impacts on various model outputs, such as radiation, cloud and aerosol properties are evaluated. Machine learning is also used to probe optimal parameter values against observations. Our findings show that using PPE is a valuable tool for climate uncertainty analysis. Furthermore, by varying many parameters simultaneously, we find that many different combinations of parameter values can produce results consistent with observations, and thus careful analysis of tuning is important. The CESM2-CAM6 PPE is publicly available, and extensible to other configurations to address questions of other model processes in the atmosphere and other model components (e.g. coupling to the land surface).

Machine learning↗