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At least 469 records · Page 26

Incorporating a completely renormalized coupled cluster approach into a composite method for thermodynamic properties and reaction paths

The correlation consistent composite approach (ccCA), using the S4 complete basis set two-point extrapolation scheme (ccCA-S4), has been modified to incorporate the left-eigenstate completely renormalized coupled cluster method, including singles, doubles, and non-iterative triples (CR-CC(2,3)) as the highest level component. The new ccCA-CC(2,3) method predicts thermodynamic properties with an accuracy that is similar to that of the original ccCA-S4 method. At the same time, the inclusion of the single-reference CR-CC(2,3) approach provides a ccCA scheme that can correctly treat reaction pathways that contain certain classes of multi-reference species such as diradicals, which would normally need to be treated by more computationally demanding multi-reference methods. The new ccCA-CC(2,3) method produces a mean absolute deviation of 1.7 kcal/mol for predicted heats of formation at 298 K, based on calibration with the G2/97 set of 148 molecules, which is comparable to that of 1.0 kcal/mol obtained using the ccCA-S4 method, while significantly improving the performance of the ccCA-S4 approach in calculations involving more demanding radical and diradical species. Both the ccCA-CC(2,3) and ccCA-S4 composite methods are used to characterize the conrotatory and disrotatory isomerization pathways of bicyclo[1.1.0]butane to trans-1,3-butadiene, for which conventional coupled cluster methods, such as the CCSD(T) approach used in the ccCA-S4 model and, in consequence, the ccCA-S4 method itself might fail by incorrectly placing the disrotatory pathway below the conrotatory one. The ccCA-CC(2,3) scheme provides correct pathway ordering while providing an accurate description of the activation and reaction energies characterizing the lowest-energy conrotatory pathway. The ccCA-CC(2,3) method is thus a viable method for the analyses of reaction mechanisms that have significant multi-reference character, and presents a generally less computationally intensive alternative to true multi-reference methods, with computer costs and ease of use that are similar to those that characterize the more established, CCSD(T)-based, ccCA-S4 methodology.

36 MATERIALS SCIENCE↗

Comprehensive Solutions for Integration of Solar Resources into Grid Operations

The need for proactive closed-loop integration of uncertainty information into system operations and probability-based controls is widely recognized, but rarely implemented in system operations. Proactive integration for this project means that the information concerning expected uncertainty ranges for net load and balancing requirements, including required balancing capacity, ramping and ramp duration characteristics, will be fed back into the generation commitment and dispatch algorithms to modify their performance so that potential shortages of these characteristics can be prevented. This basic, yet important, premise is the motivating factor for this project. The achieved project goal is to demonstrate the benefit of such a system. The project quantifies future uncertainties, predicts additional system balancing needs including the prediction intervals for capacity and ramping requirements of future dispatch intervals, evaluates the impacts of uncertainties on transmission including the risk of overloads and voltage problems, and explores opportunities for intra-hour generation adjustments helping to provide more flexibility for system operators. The resulting benefits culminate in more reliable grid operation in the face of increased system uncertainty and variability caused by solar power. The project identifies that solar power does not require special separate penetration level restrictions or penalization for its intermittency. Ultimately, the collective consideration of all sources of intermittency distributed over a wide area unified with the comprehensive evaluation of various elements of balancing process, i.e. capacity, ramping, and energy requirements, help system operators more robustly and effectively balance generation against load and interchange. This project showed that doing so can facilitate more solar and other renewable resources on the grid without compromising reliability and control performance. Efforts during the project included developing and integrating advanced probabilistic solar forecasts, including distributed PV forecasts, into closed –loop decision making processes. Additionally, new uncertainty quantifications methods and tools for the direct integration of uncertainty and variability information into grid operations at the transmission and distribution levels were developed and tested. During Phase 1, project work focused heavily on the design, development and demonstration of a set of processes and tools that could reliably and efficiently incorporate solar power into California’s grid operations. In Phase 2, connectivity between the ramping analysis tools and market applications software were completed, multiple dispatch scenarios demonstrated a successful reduction of overall uncertainty and an analysis to quantify increases in system operator reliability, and the transmission and distribution system uncertainty prediction tool was introduced to system operation engineers in a live webinar. The project met its goals, the experiments prove the advancements to methods and tools, when working together, are beneficial to not only the California Independent System Operator, but the benefits are transferable to other system operators in the United States.

14 SOLAR ENERGY↗

Life-cycle analysis of integrated biorefineries with co-production of biofuels and bio-based chemicals: co-product handling methods and implications: Co-product handling methods and implications of life-cycle analysis of biofuel and bio-chemical co-producing biorefineries

New integrated biorefinery (IBR) concepts are being investigated to co-produce hydrocarbon fuels and high-value bio-based chemicals to improve the economic viability of IBRs, to enhance biomass resource utilization efficiencies, and to maximize potential greenhouse gas (GHG) emission reductions. Unlike fuel-only biorefineries, IBRs may co-produce a significant amount of bio-based chemicals, whose emission implications for specific biorefinery products and the biorefinery as a whole need to be evaluated. We discuss this in principle and apply three sets of co-product handling methods to conduct life-cycle analysis (LCA) of modeled IBRs with co-production of two bioproduct examples - succinic acid and adipic acid - alongside a renewable diesel blendstock fuel product. The LCA results for the specific co-product handling methods that were examined shed light on potential artifacts of product-specific LCA with selected co-product methods. We discuss the advantages and limitations of each method and conclude that (i) a system-level or 'black-box' LCA allocation method is too simplistic to reflect appropriately the GHG burdens of distinctly different processing trains for fuels and chemicals in the IBR context, and (ii) the displacement method is the only co-product handling method that accounts fully for the emission effects of both the fuel product and the non-fuel bio-based co-products in the IBRs within the context of the existing fuel-focused GHG regulatory framework. Alternatively, biorefinery system-level LCA combines benefits of individual products to offer a complete picture. This system-level LCA approach offers a holistic LCA without somewhat arbitrary decisions either on an allocation basis or by the selection of an evaluation metric based on specific products.

09 BIOMASS FUELS↗

Energy-Screened Many-Body Expansion: A Practical Yet Accurate Fragmentation Method for Quantum Chemistry

We introduce an implementation of the truncated many-body expansion, MBE(n), in which the n-body corrections are screened using the effective fragment potential force field, and only those that exceed a specified energy threshold are computed at a quantum-mechanical level of theory. This energy-screened MBE(n) approach is tested at the n = 3 level for a sequence of water clusters, (H2O) N=6–34 . A threshold of 0.25 kJ/mol eliminates more than 80% of the subsystem electronic structure calculations and is even more efficacious in that respect than is distance-based screening. Even so, the energy-screened MBE(3) method is faithful to a full-system quantum chemistry calculation to within 1–2 kJ/mol/monomer, even in good quality basis sets such as aug-cc-pVTZ. These errors can be reduced by means of a two-layer approach that involves a Hartree–Fock calculation for the entire cluster. Such a correction proves to be necessary in order to obtain accurate relative energies for conformational isomers of (H2O)20, but the cost of a full-system Hartree–Fock calculation remains smaller than the cost of three-body subsystem calculations at correlated levels of theory. At the level of second-order Møller–Plesset perturbation theory (MP2), a screened MBE(3) calculation plus a full-system Hartree–Fock calculation is less expensive than a full-system MP2 calculation starting at N = 12 water molecules. This is true even if all MBE(3) subsystem calculations are performed on a single 40-core compute node, i.e., without significant parallelization. Energy-screened MBE(n) thus provides a fragment-based method that is accurate, stable in large basis sets, and low in cost, even when the latter is measured in aggregate computer time.

74 ATOMIC AND MOLECULAR PHYSICS↗

Approaching the complete-basis limit with a truncated many-body expansion

High-accuracy electronic structure calculations with correlated wave functions demand the use of large basis sets and complete-basis extrapolation, but the accuracy of fragment-based quantum chemistry methods has most often been evaluated using double-ζ basis sets, with errors evaluated relative to a supersystem calculation using the same basis set. Here, we examine the convergence towards the basis-set limit of two- and three-body expansions of the energy, for water clusters and ion–water clusters, focusing on calculations at the level of second-order Møller-Plesset perturbation theory (MP2). Several different corrections for basis-set superposition error (BSSE), each consistent with a truncated many-body expansion, are examined as well. We present a careful analysis of how the interplay of errors (from all sources) influences the accuracy of the results. We conclude that fragment-based methods often benefit from error cancellation wherein BSSE offsets both incompleteness of the basis set as well as higher-order many-body effects that are neglected in a truncated many-body expansion. An n-body counterpoise correction facilitates smooth extrapolation to the MP2 basis-set limit, and at n = 3 affords accurate results while requiring calculations in subsystems no larger than trimers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing primordial non-Gaussianity: the 3D Bispectrum of Ly-α forest and the redshifted 21-cm signal from the post reionization epoch

We explore possibility of using the three dimensional bispectra of the Ly-α forest and the redshifted 21-cm signal from the post-reionization epoch to constrain primordial non-Gaussianity. Both these fields map out the large scale distribution of neutral hydrogen and maybe treated as tracers of the underlying dark matter field. We first present the general formalism for the auto and cross bispectrum of two arbitrary three dimensional biased tracers and then apply it to the specific case. We have modeled the 3D Ly-α transmitted flux field as a continuous tracer sampled along 1D skewers which corresponds to quasars sight lines. For the post reionization 21-cm signal we have used a linear bias model. We use a Fisher matrix analysis to present the first prediction for bounds on f{sub NL} and the other bias parameters using the three dimensional 21-cm bispectrum and other cross bispectra. The bounds on f{sub NL} depend on the survey volume, and the various observational noises. We have considered a BOSS like Ly-α survey where the average number density of quasars n-bar = 10{sup −3}Mpc{sup −2} and the spectra are measured at a 2-σ level. For the 21-cm signal we have considered a 4000 hrs observation with a futuristic SKA like radio array. We find that bounds on f{sub NL} obtained in our analysis (6 ≤ Δf{sub NL} ≤ 65) is competitive with CMBR and galaxy surveys and may prove to be an important alternative approach towards constraining primordial physics using future data sets. Further, we have presented a hierarchy of power of the bispectrum-estimators towards detecting the f{sub NL}. Given the quality of the data sets, one may use this method to optimally choose the right estimator and thereby provide better constraints on f{sub NL}. We also find that by combining the various cross-bispectrum estimators it is possible to constrain f{sub NL} at a level Δf{sub NL} ∼ 4.7. For the equilateral and orthogonal template we obtain Δf{sub NL}{sup equ} ∼ 17 and Δf{sub NL}{sup orth} ∼ 13 respectively for the combined estimator. This shall be important in the quest towards understanding the mechanism behind the generation of primordial perturbations.

79 ASTRONOMY AND ASTROPHYSICS↗

Assessing the density functional theory-based multireference configuration interaction (DFT/MRCI) method for transition metal complexes

We report an assessment of the performance of density functional theory-based multireference configuration interaction (DFT/MRCI) calculations for a set of 3d- and 4d-transition metal (TM) complexes. The DFT/MRCI results are compared to published reference data from reliable high-level multi-configurational ab initio studies. The assessment covers the relative energies of different ground-state minima of the highly correlated CrF{sub 6} complex, the singlet and triplet electronically excited states of seven typical TM complexes (MnO{sub 4}{sup −}, Cr(CO){sub 6}, [Fe(CN){sub 6}]{sup 4−}, four larger Fe and Ru complexes), and the corresponding electronic spectra (vertical excitation energies and oscillator strengths). It includes comparisons with results from different flavors of time-dependent DFT (TD-DFT) calculations using pure, hybrid, and long-range corrected functionals. The DFT/MRCI method is found to be superior to the tested TD-DFT approaches and is thus recommended for exploring the excited-state properties of TM complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Weak Form Scientific Machine Learning: Test Function Construction for System Identification

Weak form Scientific Machine Learning (WSciML) is a recently developed framework for data-driven modeling and scientific discovery. It leverages the weak form of equation error residuals to provide enhanced noise robustness in system identification via convolving model equations with test functions, reformulating the problem to avoid direct differentiation of data. The performance, however, relies on wisely choosing a set of compactly supported test functions. In this work, we mathematically motivate a novel data-driven method for constructing Single-scale-Local reference functions for creating the set of test functions. Our approach numerically approximates the integration error introduced by the quadrature and identifies the support size for which the error is minimal, without requiring access to the model parameter values. Through numerical experiments across various models, noise levels, and temporal resolutions, we demonstrate that the selected supports consistently align with regions of minimal parameter estimation error. We also compare the proposed method against the strategy for constructing Multi-scale-Global (and orthogonal) test functions introduced in our prior work, demonstrating the improved computational efficiency.

FOS: Computer and information sciences↗

Manifold learning for coarse-graining atomistic simulations: Application to amorphous solids

In this work, we introduce a generalized machine learning framework to probabilistically parameterize upper-scale models in the form of nonlinear PDEs consistent with a continuum theory, based on coarse-grained atomistic simulation data of mechanical deformation and flow processes. The proposed framework utilizes a hypothesized coarse-graining methodology with manifold learning and surrogate-based optimization techniques. Coarse-grained high-dimensional data describing quantities of interest of the multiscale models are projected onto a nonlinear manifold whose geometric and topological structure is exploited for measuring behavioral discrepancies in the form of manifold distances. A surrogate model is constructed using Gaussian process regression to identify a mapping between stochastic parameters and distances. Derivative-free optimization is employed to adaptively identify a unique set of parameters of the upper-scale model capable of rapidly reproducing the system's behavior while maintaining consistency with coarse-grained atomic-level simulations. The proposed method is applied to learn the parameters of the shear transformation zone (STZ) theory of plasticity that describes plastic deformation in amorphous solids as well as coarse-graining parameters needed to translate between atomistic and continuum representations. We show that the methodology is able to successfully link coarse-grained microscale simulations to macroscale observables and achieve a high-level of parity between the models across scales.

36 MATERIALS SCIENCE↗

Benchmark calculations on the lowest-energy singlet, triplet, and quintet states of the four-electron harmonium atom

For a wide range of confinement strengths ω, explicitly-correlated calculations afford approximate energies E(ω) of the ground and low-lying excited states of the four-electron harmonium atom that are within few μhartree of the exact values, the errors in the respective energy components being only slightly higher. This level of accuracy constitutes an improvement of several orders of magnitude over the previously published data, establishing a set of benchmarks for stringent calibration and testing of approximate electronic structure methods. Its usefulness is further enhanced by the construction of differentiable approximants that allow for accurate computation of E(ω) and its components for arbitrary values of ω. The diversity of the electronic states in question, which involve both single- and multideterminantal first-order wavefunctions, and the availability of the relevant natural spinorbitals and their occupation numbers make the present results particularly useful in research on approximate density-matrix functionals. The four-electron harmonium atom is found to possess the {sup 3}P{sub +} triplet ground state at strong confinements and the {sup 5}S{sub −} quintet ground state at the weak ones, the energy crossing occurring at ω ≈ 0.0240919.

74 ATOMIC AND MOLECULAR PHYSICS↗

Testing approximate predictions of displacements of cosmological dark matter halos

We present a test to quantify how well some approximate methods, designed to reproduce the mildly non-linear evolution of perturbations, are able to reproduce the clustering of DM halos once the grouping of particles into halos is defined and kept fixed. The following methods have been considered: Lagrangian Perturbation Theory (LPT) up to third order, Truncated LPT, Augmented LPT, MUSCLE and COLA. The test runs as follows: halos are defined by applying a friends-of-friends (FoF) halo finder to the output of an N-body simulation. The approximate methods are then applied to the same initial conditions of the simulation, producing for all particles displacements from their starting position and velocities. The position and velocity of each halo are computed by averaging over the particles that belong to that halo, according to the FoF halo finder. This procedure allows us to perform a well-posed test of how clustering of the matter density and halo density fields are recovered, without asking to the approximate method an accurate reconstruction of halos. We have considered the results at z =0,0.5,1, and we have analysed power spectrum in real and redshift space, object-by-object difference in position and velocity, density Probability Distribution Function (PDF) and its moments, phase difference of Fourier modes. We find that higher LPT orders are generally able to better reproduce the clustering of halos, while little or no improvement is found for the matter density field when going to 2LPT and 3LPT. Augmentation provides some improvement when coupled with 2LPT, while its effect is limited when coupled with 3LPT. Little improvement is brought by MUSCLE with respect to Augmentation. The more expensive particle-mesh code COLA outperforms all LPT methods, and this is true even for mesh sizes as large as the inter-particle distance. This test sets an upper limit on the ability of these methods to reproduce the clustering of halos, for the cases when these objects are reconstructed at the object-by-object level.

79 ASTRONOMY AND ASTROPHYSICS↗

Automatic 3D image registration for nano-resolution chemical mapping using synchrotron spectro-tomography

Nano-resolution synchrotron X-ray spectro-tomography has been demonstrated as a powerful tool for probing the three-dimensional (3D) structural and chemical heterogeneity of a sample. By reconstructing a number of tomographic data sets recorded at different X-ray energy levels, the energy-dependent intensity variation in every given voxel fingerprints the corresponding local chemistry. The resolution and accuracy of this method, however, could be jeopardized by non-ideal experimental conditions, e.g. instability in the hardware system and/or in the sample itself. Herein is presented one such case, in which unanticipated sample deformation severely degrades the data quality. Here, to address this issue, an automatic 3D image registration method is implemented to evaluate and correct this effect. The method allows the redox heterogeneity in partially delithiated Li x Ta 0.3 Mn 0.4 O 2 battery cathode particles to be revealed with significantly improved fidelity.

3D image registration↗

SU-F-T-350: Continuous Leaf Optimization (CLO) for IMRT Leaf Sequencing

Purpose: To study a new step-and-shoot IMRT leaf sequencing model that avoids the two main pitfalls of conventional leaf sequencing: (1) target fluence being stratified into a fixed number of discrete levels and/or (2) aperture leaf positions being restricted to a discrete set of locations. These assumptions induce error into the sequence or reduce the feasible region of potential plans, respectively. Methods: We develop a one-dimensional (single leaf pair) methodology that does not make assumptions (1) or (2) that can be easily extended to a multi-row model. The proposed continuous leaf optimization (CLO) methodology takes in an existing set of apertures and associated intensities, or solution “seed,” and improves the plan without the restrictiveness of 1or (2). It then uses a first-order descent algorithm to converge onto a locally optimal solution. A seed solution can come from models that assume (1) and (2), thus allowing the CLO model to improve upon existing leaf sequencing methodologies. Results: The CLO model was applied to 208 generated target fluence maps in one dimension. In all cases for all tested sequencing strategies, the CLO model made improvements on the starting seed objective function. The CLO model also was able to keep MUs low. Conclusion: The CLO model can improve upon existing leaf sequencing methods by avoiding the restrictions of (1) and (2). By allowing for more flexible leaf positioning, error can be reduced when matching some target fluence. This study lays the foundation for future models and solution methodologies that can incorporate continuous leaf positions explicitly into the IMRT treatment planning model. Supported by Cancer Prevention & Research Institute of Texas (CPRIT) - ID RP150485.

60 APPLIED LIFE SCIENCES↗

GDB-9-Ex_EOM-CCSD: Dataset containing Equation of Motion Coupled Cluster (EOM-CCSD) calculations for organic molecules of the GDB-9-Ex dataset.

This dataset contains data-intensive quantum chemical electronic structure calculations for 80,593 organic molecules of the GDB-9-Ex dataset. Calculations were performed using the Equation of Motion Coupled Cluster (EOM-CCSD) first principles method using the ORCA software. It provides UV-vis spectra calculations of molecules with a high level of accuracy. The optical spectra behavior was collected based on the optimized molecular geometries in the DFTB method with 3ob parameters. All calculations utilized the def2-TZVP basis sets with the auxiliary def2/J and def2-TZVP/C basis sets. The similarity-transformed EOM-CCSD method that used domain-based local pair natural orbitals (DLPNO) approximation which constitutes the STEOM-DLPNO-CCSD method was used. This method is based on the STEOM approach and was found to make accurate predictions of transition energies for organic molecules. For the excitation energy calculations, the lowest 50 excitation states were calculated.

AI dataset↗

GDB-9-Ex_TD-DFT-PBE0: Dataset containing Time Dependent Density Functional Theory (TDDFT) calculations for organic molecules of the GDB-9-Ex dataset.

This dataset contains data-intensive quantum chemical electronic structure calculations for 96,766 organic molecules of the GDB-9-Ex dataset. Calculations were performed using the Time Dependent Density Functional Theory (TDDFT) first principles method using the ORCA software. It provides UV-vis spectra calculations of molecules with a high level of accuracy. The optical spectra behavior was collected based on the optimized molecular geometries in the DFTB method with 3ob parameters. All calculations utilized the def2-TZVP basis sets with the auxiliary def2/J and def2-TZVP/C basis sets. The time-dependent density-functional theory (TDDFT) approach with the PBE0 exchange-correlation functional and ORCAs default integration grid was employed. For the excitation energy calculations, the lowest 50 excitation states were calculated.

AI dataset↗

SU-E-T-152: Error Sensitivity and Superiority of a Protocol for 3D IMRT Quality Assurance

Purpose: To test if the parameters included in our 3D QA protocol with current tolerance levels are able to detect certain errors and show the superiority of 3D QA method over single ion chamber measurements and 2D gamma test by detecting most of the introduced errors. The 3D QA protocol parameters are: TPS and measured average dose difference, 3D gamma test with 3mmDTA/3% test parameters, and structure volume for which the TPS predicted and measured absolute dose difference is greater than 6%. Methods: Two prostate and two thoracic step-and-shoot IMRT patients were investigated. The following errors were introduced to each original treatment plan: energy switched from 6MV to 10MV, linac jaws retracted to 15cmx15cm, 1,2,3 central MLC leaf pairs retracted behind the jaws, single central MLC leaf put in or out of the treatment field, Monitor Units (MU) increased and decreased by 1 and 3%, collimator off by 5 and 15 degrees, detector shifted by 5mm to the left and right, gantry treatment angle off by 5 and 15 degrees. QA was performed on each plan using single ion chamber, 2D ion chamber array for 2D gamma analysis and using IBA's COMPASS system for 3D QA. Results: Out of the three tested QA methods single ion chamber performs the worst not detecting subtle errors. 3D QA proves to be the superior out of the three methods detecting all of introduced errors, except 10MV and 1% MU change, and MLC rotated (those errors were not detected by any QA methods tested). Conclusion: As the way radiation is delivered evolves, so must the QA. We believe a diverse set of 3D statistical parameters applied both to OAR and target plan structures provides the highest level of QA.

07 ISOTOPE AND RADIATION SOURCES↗

TDCOSMO VIII. A key test of systematics in the hierarchical method of time-delay cosmography

The largest source of systematic errors in the time-delay cosmography method likely arises from the lens model mass distribution, where an inaccurate choice of model could in principle bias the value of $H$ 0 . A Bayesian hierarchical framework has been proposed which combines lens systems with kinematic data, constraining the mass profile shape at a population level. The framework has been previously validated using a small sample of lensing galaxies drawn from hydro-simulations. The goal of this work is to expand the validation to a more general set of lenses consistent with observed systems, as well as confirm the capacity of the method to combine two lens populations: one which has time delay information and one which lacks time delays and has systematically different image radii. For this purpose, we generated samples of analytic lens mass distributions made of baryons+dark matter and fit the subsequent mock images with standard power-law models. Corresponding kinematics data were also emulated. The hierarchical framework applied to an ensemble of time-delay lenses allowed us to correct the $H$ 0 bias associated with model choice to find $H$ 0 within 1.5σ of the fiducial value. We then combined this set with a sample of corresponding lens systems which have no time delays and have a source at lower $z$, resulting in a systematically smaller image radius relative to their effective radius. The hierarchical framework has successfully accounted for this effect, recovering a value of $H$ 0 which is both more precise (σ ~ 2%) and more accurate (0.7% median offset) than the time-delay set alone. This result confirms that non-time-delay lenses can nonetheless contribute valuable constraining power to the determination of $H$ 0 via their kinematic constraints, assuming they come from the same global population as the time-delay set.

79 ASTRONOMY AND ASTROPHYSICS↗

Large Deviations for Level Sets of a Branching Brownian Motion and Gaussian Free Fields

We study deviation probabilities for the number of high positioned particles in branching Brownian motion and confirm a conjecture of Derrida and Shi. We also solve the corresponding problem for the two-dimensional discrete Gaussian free field. Our method relies on an elementary inequality for inhomogeneous Galton–Watson processes.

97 MATHEMATICS AND COMPUTING↗