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At least 523 records · Page 29

Fluid-Kinetic Coupling: Advanced Discretizations for Simulations on Emerging Heterogeneous Architectures (LDRD FY20-0643)

Plasma physics simulations are vital for a host of Sandia mission concerns, for fundamental science, and for clean energy in the form of fusion power. Sandia's most mature plasma physics simulation capabilities come in the form of particle-in-cell (PIC) models and magnetohydrodynamics (MHD) models. MHD models for a plasma work well in denser plasma regimes when there is enough material that the plasma approximates a fluid. PIC models, on the other hand, work well in lower-density regimes, in which there is not too much to simulate; error in PIC scales as the square root of the number of particles, making high-accuracy simulations expensive. Real-world applications, however, almost always involve a transition region between the high-density regimes where MHD is appropriate, and the low-density regimes for PIC. In such a transition region, a direct discretization of Vlasov is appropriate. Such discretizations come with their own computational costs, however; the phase-space mesh for Vlasov can involve up to six dimensions (seven if time is included), and to apply appropriate homogeneous boundary conditions in velocity space requires meshing a substantial padding region to ensure that the distribution remains sufficiently close to zero at the velocity boundaries. Moreover, for collisional plasmas, the right-hand side of the Vlasov equation is a collision operator, which is non-local in velocity space, and which may dominate the cost of the Vlasov solver. The present LDRD project endeavors to develop modern, foundational tools for the development of continuum-kinetic Vlasov solvers, using the discontinuous Petrov-Galerkin (DPG) methodology, for discretization of Vlasov, and machine-learning (ML) models to enable efficient evaluation of collision operators. DPG affords several key advantages. First, it has a built-in, robust error indicator, allowing us to adapt the mesh in a very natural way, enabling a coarse velocity-space mesh near the homogeneous boundaries, and a fine mesh where the solution has fine features. Second, it is an inherently high-order, high-intensity method, requiring extra local computations to determine so-called optimal test functions, which makes it particularly suited to modern hardware in which floating-point throughput is increasing at a faster rate than memory bandwidth. Finally, DPG is a residual-minimizing method, which enables high-accuracy computation: in typical cases, the method delivers something very close to the $L^2$ projection of the exact solution. Meanwhile, the ML-based collision model we adopt affords a cost structure that scales as the square root of a standard direct evaluation. Moreover, we design our model to conserve mass, momentum, and energy by construction, and our approach to training is highly flexible, in that it can incorporate not only synthetic data from direct-simulation Monte Carlo (DSMC) codes, but also experimental data. We have developed two DPG formulations for Vlasov-Poisson: a time-marching, backward-Euler discretization and a space-time discretization. We have conducted a number of numerical experiments to verify the approach in a 1D1V setting. In this report, we detail these formulations and experiments. We also summarize some new theoretical results developed as part of this project (published as papers previously): some new analysis of DPG for the convection-reaction problem (of which the Vlasov equation is an instance), a new exponential integrator for DPG, and some numerical exploration of various DPG-based time-marching approaches to the heat equation. As part of this work, we have contributed extensively to the Camellia open-source library; we also describe the new capabilities and their usage. We have also developed a well-documented methodology for single-species collision operators, which we applied to argon and demonstrated with numerical experiments. We summarize those results here, as well as describing at a high level a design extending the methodology to multi-species operators. We have released a new open-source library, MLC, under a BSD license; we include a summary of its capabilities as well.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Electrochemical dynamics of imidazolium ionic liquids at graphene electrodes for energy storage applications

Electric double layer capacitors (EDLCs) are prominent energy storage systems that constitute the foundation of more reliable and sustainable energy infrastructures. Modern EDLCs often incorporate ionic liquids (ILs) as a key component in their electrolytes, leveraging the high electrochemical stability of ILs to enhance device performance. The performance and functionality of these capacitors also hinge on the interfacial behavior of ILs at electrode surfaces, which remain insufficiently understood. Here, we performed synchrotron infrared nanospectroscopy (SINS) in combination with density functional theory (DFT) calculations to investigate the electric double layers (EDLs) of three imidazolium-based ILs in a custom-designed graphene liquid cell. This approach revealed new insights into the dynamics of IL EDLs and the underpinning factors originating from the IL structures. Variations in anion size and structure were found to tune the ILs’ ability to form EDLs with compact and closely-correlated ion arrangements, which are critical for enhancing their capacitive performance. These findings highlight the intricate interactions between ions governed by their structures and charge behaviors, which underscores the opportunities for targeted design of IL-based electrolytes to optimize EDLC functionality.

Electric double layers↗

NbTaV_BCC_SolidSolution_128atoms_VASP6

We performed density functional theory (DFT) calculations for body-centered-cubic (BCC) structures with 128 lattices sites of solid solution ternary alloys niobium-tantalum-vanadium (Nb-Ta-V). The first-principle code that has been used to run the calculations is the closed-source Vienna Ab-Initio Simulation Package (VASP). The calculations have been collected by sampling chemical compositions across the entire compositional range. The chemical compositions have been sampled by progressively changing the number of atoms per constituent by 8. For each chemical composition of binaries and ternaries, the first-principle calculations have been run for 100 randomized arrangements of the constituents on the BCC lattice sites. We collected data for a total of 10,500 randomized atomic structures over 105 chemical compositions. The calculations have been collected on NERSC-Perlmutter using the VASP 6.3.2. The VASP calculations for every atomic structure have been performed in 2 main steps: 1. Starting from an ideal body-centered-cubic (BCC) structure, geometry optimization with low precision has been executed to perform a preliminary optimization of the atomic structure. The output for this calculations is available in the files 0.CONTCAR, 0.OUTCAR, rlx1.out. 2. Using the atomic structure resulting from the preliminary geometry optimization, a second geometry optimization has been performed using normal precision. The output for this calculations is available in the files CONTCAR, OUTCAR, rlx2.out, vaspout.h5, and vasprun.xml. Every chemical composition sampled across the composition range in the dataset has its own directory. The convention used to name the directories for ternary alloys is AXBYCZ, where A, B, and C refer to the constituents, and X, Y, and Z are positive integers that represent the number of atoms for each constituent and their values still sum up to 128. Each atomic structure associated with a specific chemical composition has its own sub-directory within the directory of the corresponding chemical composition. The sub-directories for each atomic structure for each chemical composition are named 'case-*', where * is a positive integer that spans all the values from 1 through 100, extremes included. The files contained in each sub-directory 'case-*' for each atomic structure are as follows: 1. INCAR: input file that contains various parameters and settings for controlling the behavior of the electronic structure calculations 2. 0.POSCAR: input file that defines the atomic structure of a system 3. 0.CONTCAR: output file that provides the atomic positions and cell parameters after the first geometry optimization has been run with the precision variable set to PREC=Low in the INCAR file 4. 0.OUTCAR: output file that contains detailed information about the progress of a calculation after the first geometry optimization has been run with the precision variable set to PREC=Low in the INCAR file 5. rlx1.out: file with diagnostic information about the execution of the first geometry optimization with precision variable set to PREC=Low in the INCAR file 6. POSCAR: input file that defines the atomic structure of a system after the first geometry optimization has been run at low precision. This represents the input for the second geometry optimization run with the precision variable set to PREC=Normal in the INCAR file 7. CONTCAR: output file that provides the atomic positions and cell parameters after the second geometry optimization has been run with the precision variable set to PREC=Normal in the INCAR file 8. OUTCARL: output file that contains detailed information about the progress of a calculation after the second geometry optimization has been run with the precision variable set to PREC=Normal in the INCAR file 9. rlx2.out: file with diagnostic information about the execution of the second geometry optimization with precision variable set to PREC=Normal in the INCAR file 10. vaspout.h5: hierarchical HDF5 file containing the inputs and outputs of a VASP calculation. To analyze the data in this file we recommend using py4vasp. This file is only produced if the VASP version used is compiled with HDF5 support 11. vasprun.xml: contains similar information to OUTCAR, but in an xml format. This research is sponsored by the Artificial Intelligence Initiative as part of the Laboratory Directed Research and Development (LDRD) Program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the US Department of Energy under contract DE-AC05-00OR22725. This work used resources of the Oak Ridge Leadership Computing Facility, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725, under Directorate Discretionary awards MAT025 (Materials Science) and LRN026 (Machine Learning), and INCITE award MAT201. This work also used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, under award ERCAP0025216.

36 MATERIALS SCIENCE↗

Supramolecular Assembly of One-Dimensional Coordination Polymers for Efficient Separation of Xenon and Krypton

Efficient separation and purification of xenon (Xe) from krypton (Kr) represent an industrially crucial but challenging process. While the adsorption-based separation of these atomic gases represents an energy-efficient process, achieving highly selective adsorbents remains a difficult task. Here, we demonstrate a supramolecular assembly of coordination polymers, termed as M(II)-dhbq (M = Mg, Mn, Co, and Zn; dhbq = 2,5-dihydroxy-1,4-benzoquinone), with high-density open metal sites (5.3 nm –3 ) and optimal pore size (5.5 Å), which are able to selectively capture Xe among other chemically inert gases including Kr, Ar, N 2 , and O 2 . Among M(II)-dhbq materials, Mn-dhbq exhibits the highest Xe uptake capacity of 3.1 mmol/g and a Xe/Kr selectivity of 11.2 at 298 K and 1.0 bar, outperforming many state-of-the-art adsorbents reported so far. Remarkably, the adsorption selectivity of Mn-dhbq for Xe/O 2 , Xe/N 2 , and Xe/Ar at ambient conditions reaches as high as 70.0, 139.3, and 64.0, respectively. Direct breakthrough experiments further confirm that all M(II)-dhbq materials can efficiently discriminate Xe atoms from other inert gases. Furthermore, it is revealed from the density functional theory calculations that the strong affinity between Xe and the coordination polymer is mainly attributed to the polarization by open metal sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Soft and transferable pseudopotentials from multi-objective optimization

Ab initio pseudopotentials are a linchpin of modern molecular and condensed matter electronic structure calculations. In this work, we employ multi-objective optimization to maximize pseudopotential softness while maintaining high accuracy and transferability. To accomplish this, we develop a formulation in which softness and accuracy are simultaneously maximized, with accuracy determined by the ability to reproduce all-electron energy differences between Bravais lattice structures, whereupon the resulting Pareto frontier is scanned for the softest pseudopotential that provides the desired accuracy in established transferability tests. We employ an evolutionary algorithm to solve the multi-objective optimization problem and apply it to generate a comprehensive table of optimized norm-conserving Vanderbilt (ONCV) pseudopotentials (https://github.com/SPARC-X/SPMS-psps). Here, we show that the resulting table is softer than existing tables of comparable accuracy, while more accurate than tables of comparable softness. The potentials thus afford the possibility to speed up calculations in a broad range of applications areas while maintaining high accuracy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Dynamic Metal–Support Interaction Dictates Cu Nanoparticle Sintering on Al 2 O 3 Surfaces

Nanoparticle sintering remains a critical challenge in heterogeneous catalysis. In this work, we present a unified deep potential (DP) model based on the Perdew–Burke–Ernzerhof approximation of density functional theory for Cu nanoparticles on three Al 2 O 3 surfaces (γ-Al 2 O 3 (100), γ-Al 2 O 3 (110), and α-Al 2 O 3 (0001)). Using DP-accelerated simulations, we reveal that the nanoparticle size-mobility relationship strongly depends on the supporting surface. The diffusion of nanoparticles on the two γ-Al 2 O 3 surfaces is almost independent of the size of the nanoparticle, while the diffusion on α-Al 2 O 3 (0001) decreases rapidly with increasing size. Interestingly, nanoparticles with fewer than 55 atoms diffuse several times faster on α-Al 2 O 3 (0001) than on γ-Al 2 O 3 (100) at 800 K while expected to be more sluggish based on their larger binding energy at 0 K. The diffusion on α-Al 2 O 3 (0001) is facilitated by dynamic metal–support interaction (MSI), where Al atoms move out of the surface plane to optimize contact with the nanoparticle and relax back to the plane as the nanoparticle moves away. In contrast, the MSI on γ-Al 2 O 3 (100) and on γ-Al 2 O 3 (110) is dominated by more stable and directional Cu–O bonds, consistent with the limited diffusion observed on these surfaces. Our extended MD simulations provide insight into the sintering processes, showing that the dispersity of the nanoparticles strongly influences the coalescence driven by nanoparticle diffusion. We observed that the coalescence of Cu 13 nanoparticles on α-Al 2 O 3 (0001) can occur in a short time (10 ns) at 800 K even with an initial internanoparticle distance increased to 3 nm, while the coalescence on the two γ-Al 2 O 3 surfaces are inhibited significantly by increasing the initial internanoparticle distance. These findings demonstrate that the dynamics of the supporting surface is crucial to understanding the sintering mechanism and offer guidance for designing sinter-resistant catalysts by engineering the support morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atlas of putative minima and low-lying energy networks of water clusters n = 3 - 25

We report a database consisting of the putative minima and ~3.2 million local minima lying within 5 kcal/mol from the putative minima for water clusters of sizes n = 3 – 25 using an improved version of the Monte Carlo Temperature Basin Paving (MCTBP) global optimization procedure in conjunction with the ab-initio based, flexible, polarizable Thole-Type Model (TTM2.1-F, version 2.1) interaction potential for water. Several of the low-lying structures, as well as lowlying penta-coordinated water networks obtained with the TTM2.1-F potential, were further refined at the Møller-Plesset second order perturbation MP2/aug-cc-pVTZ level of theory. In total, we have identified 3,138,303 networks corresponding to local minima of the clusters n = 3 – 25, whose Cartesian coordinates and relative energies can be obtained from the webpage https://sites.uw.edu/wdbase/. Networks containing penta-coordinated water molecules start to appear at n = 11 and, quite surprisingly, are energetically close (within 1 – 3 kcal/mol) to the putative minima, a fact that has been confirmed from the MP2 calculations. This large database of water cluster minima spanning quite dissimilar hydrogen bonding networks is expected to influence the development and assessment of the accuracy of interaction potentials for water as well as lower scaling electronic structure methods (such as different density functionals). Furthermore, it can also be used in conjunction with data science approaches (including but no limited to neural networks, machine and deep learning) to understand the properties of water, nature’s most important substance.

Rakshit, Avijit↗

Toward Long-Life, Ultrahigh-Nickel Layered Oxide Cathodes for Lithium-Ion Batteries: Optimizing the Interphase Chemistry with a Dual-Functional Polymer

Boosting the Ni content in LiMO 2 (M = Ni, Co, Mn, etc.) layered oxides is a promising way to establish high-energydensity, low-cost cathodes, but the poor cathode surface stability is a daunting challenge for their practical viability. Herein, by constructing a dual-functional binder framework with a conductive polymer - polyaniline (PANI), the ultrahigh-Ni layered oxide cathode (LiNi 0.94 Co 0.06 O 2 ) exhibits significantly improved cyclability, with a capacity retention greatly increased from 47% to 81% over 1,000 cycles in full cells. It is demonstrated that the acidic species (e.g. HF) in the electrolyte can be efficiently scavenged through a protonation process of PANI, hence the cathode surface reactivity is greatly suppressed and the rock-salt phase propagation into bulk structure is considerably alleviated. Furthermore, the PANI binder system effectively prevents both the cathode-electrolyte interphase (CEI) and anode-electrolyte interphase (AEI) from degrading to a thick “triple-layer” architecture upon extensive cycling, resulting in more robust, thinner CEI and AEI with regulated interphasial chemistry. Moreover, the delocalized π-conjugated electrons along the backbone of PANI facilitate fast electron transfer and promote rate capability even at low temperatures (-20 °C). Finally, this work sheds light on rational binder engineering for developing high-energy-density lithium-ion batteries with acceptable cycle life.

25 ENERGY STORAGE↗

Substituted ALPO-5 Zeolites as Promising O 2 Sorption Pump Materials: A Density Functional Theory Study

Many chemical processes depend on having an environment that is low in oxygen partial pressure (P O2 < 100 Pa); sorption pumps are a promising route to establishing that environment by either oxygen pumping or oxygen separation from an inert gas. Near ambient sorption-based processes rely on either pressure or thermal swings, requiring no moving parts, no electricity, and neither very high nor very low temperatures. In this work, we use ab initio calculations to explore zeolites as a class of materials for sorption based oxygen pumping/separation. Our calculations indicate that while the neat ALPO-5 zeolite does not adsorb O 2 , O 2 does adsorb on zeolites selectively substituted with transition metals and metalloids and hence, can enable separation and pumping. ALPO-5 substituted with Si, Ge, Sn, Pd, Pt, Ti, V, Cr, Mn, Zr, Mo, Hf, W, Ce, and Pr provides adsorption energies ranging from -0.19 to -3.92 eV, (-) indicates exothermic process. Additionally, we provide a comprehensive understanding of what controls the adsorption energy: 1) the substi-tutions must be able to adopt an oxidation state that is more positive than the cation it replaces, and 2) the size of the pore into which the O 2 adsorbs to the wall. Additionally, we conduct a ther-modynamic analysis of a thermal swing cycle to approximate the optimal O 2 binding energy for 2 low energy O 2 pumping/separation. We find that the minimum energy cost likely occurs when the adsorption energy is in the range of 0.75 – 1.00 eV (72 – 97 kJ·mol -1 ), which corresponds to Ge, V, Pt, or Ce substituted ALPO-5.

36 MATERIALS SCIENCE↗

Electrospun Ti–Zr Oxide Heterostructures Enable Strongly Anchored Ultralow-Ir Anodes for Durable Acidic Oxygen Evolution

Proton-exchange-membrane water electrolysis (PEMWE) requires acidic oxygen-evolution-reaction (OER) anodes that combine high activity, high durability, and low Ir loading. Here, we report a Ti-Zr composite electrospun oxide (ESO) nanorod support that enables ultralow-Ir anodes for high-performance PEMWE. Zr-containing Ti oxide heterostructures stabilize anatase-rich TiO2, tune the local oxygen-coordination environment, and strengthen interfacial anchoring of IrOx under acidic anodic conditions. The electrospun nanorod network further creates an open, mechanically coherent catalyst layer that improves Ir utilization, ionomer penetration, and mass transport. At an anode loading of 0.2 mgIr cm-2, the optimized Ir/TiZr20-ESO anode delivers a PEMWE mass activity of 0.99 A mgIr-1 at 1.45 V, 28.3 and 43.0 times higher than commercial Ir black and commercial IrO2/TiO2, respectively. The same anode reaches 3.0 and 4.0 A cm-2 at 1.75 and 1.83 V, respectively, and sustains 2000 h operation at 2.0 A cm-2. Also, accelerated stress tests up to 525 hours over 31,500 cycles confirm promising long-term durability, with an insignificant performance decay of 0.4 μV per cycle. Density functional theory indicates that the Ti-Zr oxide heterostructure suppresses Ti demetallation and strengthens IrO2 interfacial binding, rationalizing the improved high-current-density stability.

25 ENERGY STORAGE↗

Enhancing glycerol electrooxidation from synergistic interactions of platinum and transition metal carbides

To effectively utilize glycerol as a fuel for electrochemical fuel cells, it is necessary to optimize catalysts for effective C-C bond cleavage and complete oxidation of reaction intermediates to achieve maximum efficiency. Here, the current work showed that the synergistic interactions of platinum (Pt) with transition metal carbide (TMC) substrates, such as tungsten carbide (WC) and tantalum carbide (TaC), fulfilled these criteria. The TMC-supported Pt catalysts showed higher activity and selectivity for complete glycerol oxidation than commercial 10 wt% Pt/C. In-situ FTIR analysis revealed that 5 wt% Pt/WC was the most effective catalyst among those tested for complete glycerol oxidation at 0.9 V vs RHE. In-situ X-ray absorption fine structure characterization and density functional theory calculations provided additional insight into the synergistic interactions for glycerol oxidation over Pt/TMC catalysts.

25 ENERGY STORAGE↗

An integrated high-throughput robotic platform and active learning approach for accelerated discovery of optimal electrolyte formulations

Solubility of redox-active molecules is an important determining factor of the energy density in redox flow batteries. However, the advancement of electrolyte materials discovery has been constrained by the absence of extensive experimental solubility datasets, which are crucial for leveraging data-driven methodologies. In this study, we design and investigate a highly automated workflow that synergizes a high-throughput experimentation platform with a state-of-the-art active learning algorithm to significantly enhance the solubility of redox-active molecules in organic solvents. Our platform identifies multiple solvents that achieve a remarkable solubility threshold exceeding 6.20 M for the archetype redox-active molecule, 2,1,3-benzothiadiazole, from a comprehensive library of more than 2000 potential solvents. Significantly, our integrated strategy necessitates solubility assessments for fewer than 10% of these candidates, underscoring the efficiency of our approach. Our results also show that binary solvent mixtures, particularly those incorporating 1,4-dioxane, are instrumental in boosting the solubility of 2,1,3-benzothiadiazole. Beyond designing an efficient workflow for developing high-performance redox flow batteries, our machine learning-guided high-throughput robotic platform presents a robust and general approach for expedited discovery of functional materials.

25 ENERGY STORAGE↗

Record high room temperature resistance switching in ferroelectric-gated Mott transistors unlocked by interfacial charge engineering

Abstract The superior size and power scaling potential of ferroelectric-gated Mott transistors makes them promising building blocks for developing energy-efficient memory and logic applications in the post-Moore’s Law era. The close to metallic carrier density in the Mott channel, however, imposes the bottleneck for achieving substantial field effect modulation via a solid-state gate. Previous studies have focused on optimizing the thickness, charge mobility, and carrier density of single-layer correlated channels, which have only led to moderate resistance switching at room temperature. Here, we report a record high nonvolatile resistance switching ratio of 38,440% at 300 K in a prototype Mott transistor consisting of a ferroelectric PbZr 0.2 Ti 0.8 O 3 gate and an R NiO 3 ( R : rare earth)/La 0.67 Sr 0.33 MnO 3 composite channel. The ultrathin La 0.67 Sr 0.33 MnO 3 buffer layer not only tailors the carrier density profile in R NiO 3 through interfacial charge transfer, as corroborated by first-principles calculations, but also provides an extended screening layer that reduces the depolarization effect in the ferroelectric gate. Our study points to an effective material strategy for the functional design of complex oxide heterointerfaces that harnesses the competing roles of charge in field effect screening and ferroelectric depolarization effects.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

An improved guess for the variational calculation of charge-transfer excitations in large systems

Ab initio quantum-chemical methods that perform well for computing the electronic ground state are not straightforwardly transferable to electronically excited states, particularly in large molecular systems. Wave function theory offers high accuracy, but is often prohibitively expensive. Methods based on time-dependent density functional theory (TD-DFT) are crucially sensitive to the chosen exchange-correlation functional (XCF) parameterization, and system-specific tuning protocols were therefore proposed to address the method's robustness. Methods based on the variational relaxation of the excited-state electron density showcased promising results for the calculation of charge-transfer excitations, but the complex shape of the electronic hypersurface makes convergence to a specific excited state much more difficult than for the ground state when standard variational techniques are applied. We address the latter aspect by providing suitable initial guesses, which we obtain by two separate constrained algorithms. Combined with the squared-gradient minimization algorithm for all-electrons relaxation in a freeze-and-release scheme (FRZ-SGM), we demonstrate that orbital-optimized density functional theory (OO-DFT) calculations can reliably converge to the charge-transfer states of interest even for large molecular systems. We test the FRZ-SGM method on a phenothiazine-anthraquinone CT excitation in a supramolecular Pd(II) coordination cage complex as a function of the cage conformation. This compound has been studied experimentally prior to our work. We compare this freeze-and-release scheme to two XCF reparameterizations, which were recently proposed as low-cost TD-DFT-based alternatives to variational methods. Two dye-semiconductor complexes, which were previously investigated in the context of photovoltaic applications, serve as a second example to investigate the convergence and stability of the FRZ-SGM approach. Our results demonstrate that FRZ-SGM provides reliable convergence for charge-transfer excited states and avoids variational collapse to lower-lying electronic states, whereas time-dependent DFT calculations with an adequate tuning procedure for the range-separation parameter provide a computationally efficient initial estimate of the corresponding energies, with a computational cost comparable to that of configuration-interaction singles (CIS) calculations.

Bogo, Nicola↗

A Generalized Variational Principle with Applications to Excited State Mean Field Theory

We present a generalization of the variational principle that is compatible with any Hamiltonian eigenstate that can be specified uniquely by a list of properties. This variational principle appears to be compatible with a wide range of electronic structure methods, including mean field theory, density functional theory, multireference theory, and quantum Monte Carlo. Like the standard variational principle, this generalized variational principle amounts to the optimization of a nonlinear function that, in the limit of an arbitrarily flexible wave function, has the desired Hamiltonian eigenstate as its global minimum. Unlike the standard variational principle, it can target excited states and select individual states in cases of degeneracy or near-degeneracy. As an initial demonstration of how this approach can be useful in practice, we employ it to improve the optimization efficiency of excited state mean field theory by an order of magnitude. With this improved optimization, we are able to demonstrate that the accuracy of the corresponding second-order perturbation theory rivals that of singles-and-doubles equation-of-motion coupled cluster in a substantially broader set of molecules than could be explored by our previous optimization methodology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Precisely computing phonons via irreducible derivatives

Computing phonons from first principles is typically considered a solved problem, yet inadequacies in existing techniques continue to yield deficient results in systems with sensitive phonons. Here, in this study, we circumvent this issue using the lone irreducible derivative (LID) and bundled irreducible derivative (BID) approaches to computing phonons via finite displacements, where the former optimizes precision via energy derivatives and the latter provides the most efficient algorithm using force derivatives. A condition number optimized basis for BID is derived which guarantees the minimum amplification of error. Additionally, a hybrid LID-BID approach is formulated, in which select irreducible derivatives computed using LID replace BID results. We illustrate our approach on two prototypical systems with sensitive phonons: the shape memory alloy AuZn and metallic lithium. Comparing our resulting phonons in the aforementioned crystals to calculations in the literature reveals nontrivial inaccuracies. Our approaches can be fully automated, making them well suited for both niche systems of interest and high-throughput approaches.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Modeling discontinuous dynamic recrystallization containing second phase particles in magnesium alloys utilizing phase field method

Pre-existing second phase particles can induce particle stimulated nucleation (PSN) and pinning effect on grain boundaries during DRX process of magnesium alloys. The interaction among pinning effect, PSN mechanism and strain-induced grain boundary migration (SIBM) nucleation mechanism imposes challenge in quantitative study of microstructure evolution. A phase field model that describes discontinuous dynamic recrystallization process considering second phase particles (PF-DDRX-SP) which mainly distribute along grain boundaries is developed. The second phase order parameter with diffusion interface is introduced to the free energy function. With considering the pinning effect of second phase particles on grain boundaries, the grain boundary energy couples the interaction between second phase and grains. The effect of second phase on dislocation density evolution is considered in the model, and the PSN and SIBM mechanism are both executed by limiting the nucleation position to the grain boundary and the second phase interface. For the validation, the initial topology consistent with initial microstructure is applied to the simulation of DRX kinetics and flow behavior of AZ80 magnesium alloy, and great reliability and accuracy of developed model is indicated. Furthermore, through the model, the microstructure evolution with different particle size and with different volume fraction of round particle during DRX process were simulated. Finally, the results show that particles with higher dispersion reduce the number of DRX nuclei, which indicate that second phase particles suppress the nucleation at grain boundaries because of the pinning effect. More importantly, the proposed model could also quantitatively predict the relationships between the parameters of second phase particles and DRX behaviors, and enable to optimize the initial second phase structure in a uniform grain structure during thermomechanical process.

36 MATERIALS SCIENCE↗

DED Additively Manufactured HEAs Optimized via Parametric Study of Functionally Graded Materials

Complex concentrated alloys (CCAs) are a system of alloys composition of nearly equiatomic elements, creating a state of high configurational entropy in the material. These alloys are of interest for various industrial applications due to their high strength and hardness, wide operational temperature range, creep and diffusion resistance, and radiation resistance. In the current work CoCrFeNi-base CCAs are synthesize by combining three commonly industrial alloys: IN718, SS316L, and 70Co30Cr (commercially known as Stellite 21), in-situ utilizing directed energy deposition (DED) additive manufacturing (AM). One bulk specimen is fabricated with a 1:1:1 ratio of IN718, SS316L, and 70Co30Cr where IN718 is a source of nickel and chrome, SS316 is a source of iron and chrome, and 70Co30Cr is a source of cobalt and supplemental chrome. Additionally, a functionally graded material (FGM) of the identified CCA system from SS316 was fabricated with 10 layers, where the initial five layers are the base material of SS316L and graded by steps of 20% to transition to the CCA system. Overall build quality, microstructure, compositional distribution, phases analysis, and microhardness were studied by laser optical microscopy, scanning election microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction analysis (XRD), and Vickers microhardness techniques. Overall build quality showed a successful bulk build with acceptable density, however unmelted particles are observed in the as-built alloy. Compositional results show that the system meets the Boltzmann’s hypothesis definition of an HEA, and that an FCC CCA was produced with increased hardness, small grain size, and superior hardness properties to the SS316L substrate. While initial XRD results show predominately FCC structure, EDS analysis of interdendritic regions show the existence of Laves phases in the material. The fabrication of an FGM CCA allowed for potential screening of additional alloy mixes which may be of interest to explore in future research, and the resulting composition is compared to predicted values. This novel method of CCA fabrication results in substantial cost savings of these CCA systems over traditional methods.

36 MATERIALS SCIENCE↗