Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “self-interaction correction”

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

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

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Spin-state gaps and self-interaction-corrected density functional approximations: Octahedral Fe(II) complexes as case study

Accurate prediction of a spin-state energy difference is crucial for understanding the spin crossover phenomena and is very challenging for density functional approximations, especially for local and semi-local approximations due to delocalization errors. Here, we investigate the effect of the self-interaction error removal from the local spin density approximation (LSDA) and Perdew–Burke–Ernzerhof generalized gradient approximation on the spin-state gaps of Fe(II) complexes with various ligands using recently developed locally scaled self-interaction correction (LSIC) by Zope et al. [J. Chem. Phys. 151, 214108 (2019)]. The LSIC method is exact for one-electron density, recovers the uniform electron gas limit of the underlying functional, and approaches the well-known Perdew–Zunger self-interaction correction (PZSIC) as a particular case when the scaling factor is set to unity. Our results, when compared with reference diffusion Monte Carlo results, show that the PZSIC method significantly overestimates spin-state gaps favoring low spin states for all ligands and does not improve upon density functional approximations. The perturbative LSIC-LSDA using PZSIC densities significantly improves the gaps with a mean absolute error of 0.51 eV but slightly overcorrects for the stronger CO ligands. Finally, the quasi-self-consistent LSIC-LSDA, such as coupled-cluster single double and perturbative triple [CCSD(T)], gives a correct sign of spin-state gaps for all ligands with a mean absolute error of 0.56 eV, comparable to that of CCSD(T) (0.49 eV).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Self-consistent implementation of locally scaled self-interaction-correction method

Recently proposed local self-interaction correction (LSIC) method is a one-electron self-interaction-correction (SIC) method that uses an iso-orbital indicator to apply the SIC at each point in space by scaling the exchange–correlation and Coulomb energy densities. The LSIC method is exact for the one-electron densities, also recovers the uniform electron gas limit of the uncorrected density functional approximation, and reduces to the well-known Perdew–Zunger SIC (PZSIC) method as a special case. This article presents the self-consistent implementation of the LSIC method using the ratio of Weizsäcker and Kohn–Sham kinetic energy densities as an iso-orbital indicator. The atomic forces as well as the forces on the Fermi-Löwdin orbitals are also implemented for the LSIC energy functional. Results show that LSIC with the simplest local spin density functional predicts atomization energies of the AE6 dataset better than some of the most widely used generalized-gradient-approximation (GGA) functional and barrier heights of the BH6 database better than some of the most widely used hybrid functionals. The LSIC method [a mean absolute error (MAE) of 0.008 Å] predicts bond lengths of a small set of molecules better than the PZSIC-LSDA (MAE 0.042 Å) and LSDA (0.011 Å). Furthermore, this work shows that accurate results can be obtained from the simplest density functional by removing the self-interaction-errors using an appropriately designed SIC method.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Vertical detachment energies of ammonia cluster anions using self-interaction-corrected methods

Systems with weakly bound extra electrons impose great challenges to semilocal density functional approximations (DFAs), which suffer from self-interaction errors. Small ammonia clusters are one such example of weakly bound anions where the extra electron is weakly bound. We applied two self-interaction correction (SIC) schemes, viz., the well-known Perdew–Zunger and the recently developed locally scaled SIC (LSIC) with the local spin density approximation (LSDA), Perdew–Burke–Ernzerhof (PBE) generalized gradient approximation (GGA), and the SCAN meta-GGA functionals to calculate the vertical detachment energies (VDEs) of small ammonia cluster anions (NH3)n–. Our results show that the LSIC significantly reduces the errors in calculations of VDE with LSDA and PBE-GGA functionals leading to better agreement with the reference values calculated with coupled cluster singles and doubles with perturbative triples [CCSD(T)]. Accurate prediction of VDE as an absolute of the highest occupied molecular orbital (HOMO) is challenging for DFAs. Our results show that VDEs estimated from the negative of HOMO eigenvalues with the LSIC-LSDA and Perdew–Zunger SIC-PBE are within 11 meV of the reference CCSD(T) results. Here, the LSIC method performs consistently well for the VDE estimates, from both the total energy differences and the absolute HOMO eigenvalues.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Comparing first-principles density functionals plus corrections for the lattice dynamics of YBa 2 Cu 3 O 6

The enigmatic mechanism underlying unconventional high-temperature superconductivity, especially the role of lattice dynamics, has remained a subject of debate. Theoretical insights have long been hindered due to the lack of an accurate first-principles description of the lattice dynamics of cuprates. Recently, using the r2SCAN meta-generalized gradient approximation (meta-GGA) functional, we have been able to achieve accurate phonon spectra of an insulating cuprate YBa 2 Cu 3 O 6 and discover significant magnetoelastic coupling in experimentally interesting Cu–O bond stretching optical modes [Ning et al., Phys. Rev. B 107, 045126 (2023)]. We extend this work by comparing Perdew–Burke–Ernzerhof and r2SCAN performances with corrections from the on-site Hubbard U and the D4 van der Waals (vdW) methods, aiming at further understanding on both the materials science side and the density functional side. We demonstrate the importance of vdW and self-interaction corrections for accurate first-principles YBa 2 Cu 3 O 6 lattice dynamics. Since r2SCAN by itself partially accounts for these effects, the good performance of r2SCAN is now more fully explained. Finally, in addition, the performances of the Tao–Mo series of meta-GGAs, which are constructed in a different way from the strongly constrained and appropriately normed (SCAN) meta-GGA and its revised version r2SCAN, are also compared and discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Downward quantum learning from element 118: Automated generation of Fermi–Löwdin orbitals for all atoms

A new algorithm based on a rigorous theorem and quantum data computationally mined from element 118 guarantees automated construction of initial Fermi–Löwdin-Orbital (FLO) starting points for all elements in the Periodic Table. It defines a means for constructing a small library of scalable FLOs for universal use in molecular and solid-state calculations. The method can be systematically improved for greater efficiency and for applications to excited states such as x-ray excitations and optically silent excitations. FLOs were introduced to recast the Perdew–Zunger self-interaction correction (PZSIC) into an explicit unitarily invariant form. The FLOs are generated from a set of N quasi-classical electron positions, referred to as Fermi-Orbital descriptors (FODs), and a set of N-orthonormal single-electron orbitals. FOD positions, when optimized, minimize the PZSIC total energy. However, creating sets of starting FODs that lead to a positive definite Fermi orbital overlap matrix has proven to be challenging for systems composed of open-shell atoms and ions. The proof herein guarantees the existence of a FLOSIC solution and further guarantees that if a solution for N electrons is found, it can be used to generate a minimum of N – 1 and a maximum of 2 N – 2 initial starting points for systems composed of a smaller number of electrons. As a result, applications to heavy and super-heavy atoms are presented. All starting solutions reported here were obtained from a solution for element 118, Oganesson.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Electronic structure simulations in the cloud computing environment

The transformative impact of modern computational paradigms and technologies, such as high-performance computing, quantum computing, and cloud computing, has opened up profound new opportunities for scientific simulations. Scalable computational chemistry is one beneficiary of this technological progress. The main focus of this paper is on the performance of various quantum chemical formulations, ranging from low-order methods to high-accuracy approaches, implemented in different computational chemistry packages, such as NWChem, NWChemEx, SPEC, ExaChem, and FLOSIC codes on the Azure Quantum Element (AQE) Microsoft cloud services. We pay particular attention to the intricate workflows for performing composite chemistry simulations, associated data curation, and mechanisms for accuracy assessment, as defined by the enabling cloud Computational Chemistry as a Service (CCaaS). Our focus also extends to Arrows' automated workflow for high throughput simulations. Finally, we provide a perspective on the role of cloud computing in supporting the mission of leadership computational facilities (LCFs).

computational chemistry, electronic structure, Clo↗
DOE OSTI2024

High-throughput determination of Hubbard $U$ and Hund $J$ values for transition metal oxides via the linear response formalism

DFT+U provides a convenient, cost-effective correction for the self-interaction error (SIE) that arises when describing correlated electronic states using conventional approximate density functional theory (DFT). The success of a DFT+U(+J) calculation hinges on the accurate determination of its Hubbard U and Hund J parameters, and the linear response (LR) methodology has proven to be computationally effective and accurate for calculating these parameters. This study provides a high-throughput computational analysis of the U and J values for transition metal d-electron states in a representative set of over 1000 magnetic transition metal oxides (TMOs), providing a frame of reference for researchers who use DFT+U to study transition metal oxides. In order to perform this high-throughput study, an ATOMATE workflow is developed for calculating U and J values automatically on massively parallel supercomputing architectures. Here, to demonstrate an application of this workflow, the spin-canting magnetic structure and unit cell parameters of the multiferroic olivine LiNiPO4 are calculated using the computed Hubbard U and Hund J values for Ni-d and O-p states, and are compared with experiment. Both the Ni-d U and J corrections have a strong effect on the Ni-moment canting angle. Additionally, including a O-pU value results in a significantly improved agreement between the computed lattice parameters and experiment

36 MATERIALS SCIENCE↗
DOE OSTI2022

Data-driven approach to parameterize SCAN + U for an accurate description of 3 d transition metal oxide thermochemistry

Semilocal density-functional theory (DFT) methods exhibit significant errors for the phase diagrams of transition-metal oxides that are caused by an incorrect description of molecular oxygen and the large self-interaction error in materials with strongly localized electronic orbitals. Empirical and semiempirical corrections based on the DFT + U method can reduce these errors, but the parameterization and validation of the correction terms remains an on-going challenge. Here we develop a systematic methodology to determine the parameters and to statistically assess the results by considering interlinked thermochemical data across a set of transition metal compounds. We consider three interconnected levels of correction terms: (1) a constant oxygen binding correction, (2) Hubbard-U correction, and (3) DFT/DFT + U compatibility correction. The parameterization is expressed as a unified optimization problem. We demonstrate this approach for 3d transition metal oxides, considering a target set of binary and ternary oxides. With a total of 37 measured formation enthalpies taken from the literature, the dataset is augmented by the reaction energies of 1710 unique reactions that were derived from the formation energies by systematic enumeration. To ensure a balanced dataset across the available data, the reactions were grouped by their similarity using clustering and suitably weighted. The parameterization is validated using leave-one-out cross validation (CV), a standard technique for the validation of statistical models. We apply the methodology to the strongly constrained and appropriately normed (SCAN) density functional. Based on the CV score, the error of binary (ternary) oxide formation energies is reduced by 40% (75%) to 0.10 (0.03) eV/atom. A simplified correction scheme that does not involve SCAN/SCAN + U compatibility terms still achieves an error reduction of 30% (25%). The method and tools demonstrated here can be applied to other classes of materials or to parameterize the corrections to optimize DFT + U performance for other target physical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Energy Frontier Research Centers: Center for the Computational Design of Functional Layered Materials (CCDM) August 1, 2014 - July 31, 2018; Center for Complex Materials from First Principles (CCM) August 1, 2018 - July 31, 2021 (Final Report)

The mission of the DOE Energy Frontier Research Centers CCDM (2014-2018) and CCM (2018-2021) was to theoretically develop, computationally apply, and experimentally validate electronic structure methods for all materials, with a focus on the complex materials, especially layered and two-dimensional materials, strongly-correlated materials, and liquid water. This was achieved by over 200 published journal articles authored by about 17 senior investigators from physics and chemistry and from theory, computation, and experiment, plus their collaborators. In particular, the Centers confirmed the predictive power of the SCAN (strongly constrained and appropriately normed) density functional, which was constructed to satisfy 17 known exact constraints and several appropriate norms. Without being fitted to real bonded systems, and at a modest computational cost, SCAN correctly predicted covalent, ionic, metallic, hydrogen, and van der Waals bonds in many challenging materials. SCAN gave an improved description of defects in semiconductors, surface properties of metals, seven phases of ice, liquid water, liquid and supercooled silicon, subtle structural distortions in ferroelectrics, formation energies and structural predictions for solids, and critical pressures for structural phase transitions. Perhaps most remarkably, SCAN correctly described some strongly-correlated materials that were previously believed to be beyond the reach of density-functional approximations. SCAN is the only density functional that correctly predicts the band gap closing under chemical doping of the cuprate high-temperature superconducting materials. SCAN also predicts a landscape of competing stripe and magnetic phases in the cuprates. For some materials with some codes, SCAN has convergence problems that are greatly reduced by the CCM-developed r 2 SCAN, without loss of accuracy or rigor. SCAN and r 2 SCAN still make some self-interaction error, which is greatly reduced by the CCDM/ CCM-developed local orbital scaling correction (LOSC). These Centers further proved that the fundamental energy gaps of a solid from an orbital energy difference and from total energy differences are the same for a large class of generalized Kohn-Sham (GKS) functionals, including SCAN and standard hybrid functionals, and that symmetry breaking arises when a dynamic density fluctuation drops to zero frequency. The Centers identified new mechanisms for catalysis in layered materials with ions intercalated between the layers, investigated charge density waves both in model systems and in real layered materials, studied changes of band gap with the number of layers, and explored topological ultrathin films, bent nanoribbons, and defects.

08 HYDROGEN↗
DOE OSTI2023

Conformal freeze-in, composite dark photon, and asymmetric reheating

Large classes of dark sector models feature mass scales and couplings very different from the ones we observe in the Standard Model (SM). Moreover, in the freeze-in mechanism, often employed by the dark sector models, it is also required that the dark sector cannot be populated during the reheating process like the SM. This is the so called asymmetric reheating. Such disparities in sizes and scales often call for dynamical explanations. In this paper, we explore a scenario in which slow evolving conformal field theories (CFTs) offer such an explanation. Building on the recent work on conformal freeze-in (COFI), we focus on a coupling between the Standard Model Hypercharge gauge boson and an anti-symmetric tensor operator in the dark CFT. We present a scenario which dynamically realizes the asymmetric reheating and COFI production. With a detailed study of dark matter production, and taking into account limits on the dark matter (DM) self-interaction, warm DM bound, and constraints from the stellar evolution, we demonstrate that the correct relic abundance can be obtained with reasonable choices of parameters. The model predicts the existence of a dark photon as an emergent composite particle, with a small kinetic mixing also determined by the CFT dynamics, which correlates it with the generation of the mass scale of the dark sector. At the same time, COFI production of dark matter is very different from those freeze-in mediated by the dark photon. This is an example of the physics in which a realistic dark sector model can often be much richer and with unexpected features.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

A tail of eternal inflation

Non-trivial inflaton self-interactions can yield calculable signatures of primordial non-Gaussianity that are measurable in cosmic surveys. We calculate the non-Gaussian corrections to Stochastic Inflation within the framework of Soft de Sitter Effective Theory, from which we derive the associated probability distribution for the scalar fluctuations. As a consequence of this new result, we show that the phase transition to slow-roll eternal inflation is often incalculable in these models. Instead, this transition is sensitive to the non-Gaussian tail of the distribution of scalar fluctuations, which probes physics inside the horizon, potentially beyond the cutoff scale of the Effective Field Theory of Inflation. We delineate the parameter space consistent with current observations and weak coupling at horizon crossing in which the large fluctuations relevant for eternal inflation can only be determined by appealing to a UV completion. We also argue that this breakdown of the perturbative description is required for the de Sitter entropy to reflect the number of de Sitter microstates.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Generating non-topological solitons via thermal corrections: Higgs balls

Scalar fields which carry charge can generally form non-topological solitons (Q-balls), if the energy in the extended configuration is less than the energy of an equivalent number of free quanta. For global Q-balls, such solitons exist whenever the potential grows slower than quadratically. We show that even in the absence of attractive interactions, finite temperature corrections can generate Q-ball solutions, as the coefficient of cubic corrections is generally negative. As an illustration of this, we consider the possibility of constructing Q-balls using the Higgs field. We first show that the finite temperature corrections would enable the existence of Higgs balls if the Standard Model symmetry was ungauged. We then consider gauged Q-balls, following [1], and demonstrate that Higgs self-interactions mediated by the Standard Model gauge bosons are sufficient to prevent the existence of these states in the actual Standard Model. However, these states can exist in a variety of extensions, as we show explicitly through an example.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Differential cross-section measurements of the production of four charged leptons in association with two jets using the ATLAS detector

Differential cross-sections are measured for the production of four charged leptons in association with two jets. These measurements are sensitive to final states in which the jets are produced via the strong interaction as well as to the purely-electroweak vector boson scattering process. The analysis is performed using proton-proton collision data collected by ATLAS at $\sqrt{s}$ = 13 TeV and with an integrated luminosity of 140 fb –1 . The data are corrected for the effects of detector inefficiency and resolution and are compared to state-of-the-art Monte Carlo event generator predictions. The differential cross-sections are used to search for anomalous weak-boson self-interactions that are induced by dimension-six and dimension-eight operators in Standard Model effective field theory.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Use of FLOSIC for understanding anion-solvent interactions

An Achille’s heel of lower-rung density-functional approximations is that the highest-occupied-molecular-orbital energy levels of anions, known to be stable or metastable in nature, are often found to be positive in the worst case or above the lowest-unoccupied-molecular-orbital levels on neighboring complexes that are not expected to accept charge. A trianionic example, [Cr(C2O4)3]3−, is of interest for constraining models linking Cr isotope ratios in rock samples to oxygen levels in Earth’s atmosphere over geological timescales. Here we describe how crowd sourcing can be used to carry out self-consistent Fermi–Löwdin–Orbital-Self-Interaction corrected calculations (FLOSIC) on this trianion in solution. The calculations give a physically correct description of the electronic structure of the trianion and water. In contrast, uncorrected local density approximation (LDA) calculations result in approximately half of the anion charge being transferred to the water bath due to the effects of self-interaction error. Use of group-theory and the intrinsic sparsity of the theory enables calculations roughly 125 times faster than our initial implementation in the large N limit reached here. By integrating charge density densities and Coulomb potentials over regions of space and analyzing core-level shifts of the Cr and O atoms as a function of position and functional, we unambiguously show that FLOSIC, relative to LDA, reverses incorrect solute-solvent charge transfer in the trianion-water complex. In comparison to other functionals investigated herein, including Hartree–Fock and the local density approximation, the FLOSIC Cr 1s eigenvalues provide the best agreement with experimental core ionization energies.

Chemistry↗
DOE OSTI2023

Loop corrections in Minkowski spacetime away from equilibrium. Part II. Finite-time results

Loop corrections to finite-time correlation functions in quantum field theories away from equilibrium can be calculated using the in-in path integral approach. In this paper, we calculate the unequal-time two-point correlator for different massless self-interacting scalar quantum field theories on a Minkowski background, starting the field evolution at an arbitrary initial time. We find the counterterms that need to be added to UV-renormalize the result, including usual in-out counterterms in the dynamics and additional initial state counterterms that are required to cancel all UV divergences. We find that the late-time limit of the renormalized correlation function exhibits a linear or logarithmic growth in time, depending on whether the interaction strength is dimension-one or dimensionless, respectively. The late-time correlations match those obtained in our companion paper and, as shown there, the divergences do not indicate a real IR issue, consistent with what one would expect in Minkowski.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Delocalization error poisons the density-functional many-body expansion

The many-body expansion is a fragment-based approach to large-scale quantum chemistry that partitions a single monolithic calculation into manageable subsystems. This technique is increasingly being used as a basis for fitting classical force fields to electronic structure data, especially for water and aqueous ions, and for machine learning. Here, we show that the many-body expansion based on semilocal density functional theory affords wild oscillations and runaway error accumulation for ion–water interactions, typified by F − (H 2 O) N with N ≳ 15. We attribute these oscillations to self-interaction error in the density-functional approximation. The effect is minor or negligible in small water clusters, explaining why it has not been noticed previously, but grows to catastrophic proportion in clusters that are only moderately larger. This behavior can be counteracted with hybrid functionals but only if the fraction of exact exchange is ≳50%, whereas modern meta-generalized gradient approximations including ωB97X-V, SCAN, and SCAN0 are insufficient to eliminate divergent behavior. Other mitigation strategies including counterpoise correction, density correction (i.e., exchange–correlation functionals evaluated atop Hartree–Fock densities), and dielectric continuum boundary conditions do little to curtail the problematic oscillations. In contrast, energy-based screening to cull unimportant subsystems can successfully forestall divergent behavior. These results suggest that extreme caution is warranted when the many-body expansion is combined with density functional theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Comparative Density Functional Theory Study of Magnetic Exchange Couplings in Dinuclear Transition-Metal Complexes

Multicenter transition-metal complexes (MCTMs) with magnetically interacting ions have been proposed as components for information-processing devices and storage units. For any practical application of MCTMs as magnetic units, it is crucial to characterize their magnetic behavior, and in particular, the isotropic magnetic exchange coupling, J, between its magnetic centers. Due to the large size of typical MCTMs, density functional theory is the only practical electronic structure method for evaluating the J coupling. Here, we assess the accuracy of different density functional approximations for predicting the magnetic couplings of eight dinuclear transition-metal complexes, including five dimanganese, two dicopper, and one divanadium with known reliable experimental J couplings spanning from ferromagnetic to strong antiferromagnetic. The density functionals considered include global hybrid functionals which mix semilocal density functional approximations and exact exchange with a fixed admixing parameter, six local hybrid functionals where the admixing parameters are extended to be spatially dependent, the SCAN and r 2 SCAN meta-generalized gradient approximations (GGAs), and two widely used GGAs. We found that global hybrids tested in this work have a tendency to over-correct the error in magnetic coupling parameters from the Perdew–Burke–Ernzerhof (PBE) GGA as seen for manganese complexes. The performance of local hybrid density functionals shows no improvement in terms of bias and is scattered without a clear trend, suggesting that more efforts are needed for the extension from global to local hybrid density functionals for this particular property. The SCAN and r 2 SCAN meta-GGAs are found to perform as well as benchmark global hybrids on most tested complexes. We further analyze the charge density redistribution of meta-GGAs as well as global and local hybrid density functionals with respect to that of PBE, in connection to the self-interaction error or delocalization error.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Machine learning for accuracy in density functional approximations

Machine learning techniques have found their way into computational chemistry as indispensable tools to accelerate atomistic simulations and materials design. In addition, machine learning approaches hold the potential to boost the predictive power of computationally efficient electronic structure methods, such as density functional theory, to chemical accuracy and to correct for fundamental errors in density functional approaches. In this paper, recent progress in applying machine learning to improve the accuracy of density functional and related approximations is reviewed. Promises and challenges in devising machine learning models transferable between different chemistries and materials classes are discussed with the help of examples applying promising models to systems far outside their training sets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗