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Results for “ab initio modeling”

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.

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At least 451 records · Page 25
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

New reactions of diazene and related species for modelling combustion of amine fuels

Potential energy surfaces for reactions involving N 2 H 2 isomers of diazene (diimide) have been explored using density functional theory, with energies based on coupled-cluster theory. A focus is on processes that create or consume these species, and isomerisation between the E (trans) and Z (cis) forms of HNNH. Furthermore, these include isomerisation and dissociation pathways for HNNH, addition of H atoms to form N 2 H 3 , abstraction by H atoms yielding short-lived NNH, and abstraction reactions of H with N 2 H 3 . Transition state and capture theories are applied for high-pressure-limiting behaviour, while low-pressure and falloff regions are characterised via the methods of Troe and coworkers. Rate constants and thermochemistry are provided to improve models of diamine chemistry, relevant to the combustion of NH 3 especially at high concentrations, high pressures or under reducing conditions. Results indicate that amine radical recombination mainly yields the E HNNH isomer, while H-abstraction from N 2 H 3 results in E HNNH and H 2 NN. However, at elevated temperature E → Z isomerisation becomes competitive, and Z HNNH, being more reactive, acts to enhance the diazene consumption rate.

10 SYNTHETIC FUELS↗
DOE OSTI2025

Thermal disorder and phonon softening in the ferroelectric phase transition of lead titanate

We report a molecular dynamics study of ab initio quality of the ferroelectric phase transition in crystalline PbTi⁢O3. We model anharmonicity accurately in terms of potential energy and polarization surfaces trained on density functional theory data with modern machine learning techniques. Our simulations demonstrate that the transition has a strong order-disorder character, in agreement with diffraction experiments, and provide fresh insight into the approach to equilibrium across the phase transition. We find that the emergence and disappearance of the macroscopic polarization is driven by dipolar switching at the nanometer scale. We also computed the infrared optical absorption spectra in both the ferroelectric and the paraelectric phases, finding good agreement with the experimental Raman frequencies. Often, the almost ideal displacive character of the soft mode detected by Raman scattering in the paraelectric phase has been contrasted with the order-disorder character of the transition suggested by diffraction experiments. We settle this issue by showing that the soft mode coexists with a strong Debye relaxation associated with thermal disordering of the dipoles. The Debye relaxation feature is centered at zero frequency and appears near the transition temperature in both the ferroelectric and the paraelectric phases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Modeling Hydrogen Evolution Reaction Kinetics through Explicit Water–Metal Interfaces

Despite the apparent simplicity of the hydrogen evolution reaction (HER) and the decades of research into it, controversy remains in the literature regarding the identity of the active site and the competition between the Heyrovsky and Tafel steps. In this work, we use charge-extrapolated ab initio simulations with explicit water in conjunction with mean-field microkinetic modeling to explore the mechanism for HER on both close-packed (111) and stepped (211) transition metals. First, we show that atop H*, beyond a monolayer of hollow H*, is unlikely to play a role in the HER mechanism, given its very positive adsorption energies. The energetics suggests the Volmer–Heyrovsky mechanism to predominate on fcc transition metals under typical operating conditions. Here, we evaluate our theoretical results vs several experimental observations. We show that the Volmer–Heyrovsky mechanism predicts an activity volcano with its peak at a H* binding ΔG H* ≈ 0 eV, consistent with experiment. In contrast, the Volmer–Tafel volcano shows a broad rate plateau between ΔG H* ≈ 0 eV and ΔG H* ≈ – 0.4 eV. We find our theoretical Tafel slopes to be consistent with experimental ones on a range of transition metals. We show that, in line with experimental observations, the introduction of a CO(g) atmosphere shifts the strong binding metals toward the weak binding leg. Our study suggests that the simple thermodynamic approach to HER activity still holds, even when a detailed kinetic picture is considered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Computational Modeling of Battery Materials

This chapter provides a broad overview of the various computational modeling techniques used to gain fundamental insights into coupled electrochemical processes that occur in battery materials at electronic-to-mesoscopic scales. Furthermore, representative successes of these techniques in modeling electrodes, electrolytes, and electrode-electrolyte interfaces are highlighted to establish the current state-of-the-art in the field.

25 ENERGY STORAGE↗
DOE OSTI2023

Interplay between magnetism and band topology in the kagome magnets R Mn 6 Sn 6

Kagome-lattice magnets R Mn 6 Sn 6 recently emerged as a new platform to exploit the interplay between magnetism and topological electronic states. Some of the most exciting features of this family are the dramatic dependence of the easy magnetization direction on the rare-earth specie, despite other magnetic and electronic properties being essentially unchanged, and the kagome geometry of the Mn planes that in principle can generate flat bands and Dirac points; gapping of the Dirac points by spin-orbit coupling has been suggested recently to be responsible for the observed anomalous Hall response in the member TbMn 6 Sn 6 . In this paper, we address both issues with ab initio calculations. We have discovered the significant role played by higher-order crystal-field parameters and rare-earth magnetic anisotropy constants in these systems. Further, we demonstrate that the microscopic origin of rare-earth magnetic anisotropy can also be quantified and understood at various levels: ab initio, phenomenological, and analytical. In particular, using a simple and physically transparent analytical model based on perturbation theory, we are able to explain, with full quantitative agreement, the evolution of rare-earth magnetic anisotropy across the series. We analyze in detail the topological properties of Mn-dominated bands and demonstrate how they emerge from the multiorbital planar kagome model. We further show that, despite this fact, most of the topological features at the Brillouin zone corner K are strongly 3D and therefore cannot explain the observed quasi-2D anomalous Hall effect, while the most pronounced quasi-2D dispersion are too far removed from the Fermi level. By employing self-consistent calculations with ab initio many-body approaches, we demonstrate that the exchange-correlation effects beyond the density functional theory for itinerant Mn- d electrons do not significantly alter the obtained electronic and magnetic structure. Therefore, we conclude that, contrary to previous claims, the most pronounced 2D kagome-derived topological band features bear little relevance to transport in RMn 6 Sn 6 , albeit they may possibly be brought to focus by electron or hole doping.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Machine learning approach for vibronically renormalized electronic band structures

Here, we present a machine learning (ML) method for efficient computation of vibrational thermal expectation values of physical properties from first principles. Our approach is based on the nonperturbative frozen phonon formulation in which stochastic Monte Carlo algorithm is employed to sample configurations of nuclei in a supercell at finite temperatures based on a first-principles phonon model. A deep-learning neural network is trained to accurately predict physical properties associated with sampled phonon configurations, thus bypassing the time-consuming ab initio calculations. To incorporate the point-group symmetry of the electronic system into the ML model, group-theoretical methods are used to develop a symmetry-invariant descriptor for phonon configurations in the supercell. We apply our ML approach to compute the temperature dependent electronic energy gap of silicon based on density functional theory (DFT). We show that, with less than a hundred DFT calculations for training the neural network model, an order of magnitude larger number of sampling can be achieved for the computation of the vibrational thermal expectation values. Our work highlights the promising potential of ML techniques for finite temperature first-principles electronic structure methods.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Ab Initio Polariton Transport Dynamics with the Classical Path Approximation

We present an ab initio framework for simulating polariton transport dynamics based on the classical path approximation (CPA). The quantum dynamics of polariton transport involves simulating many electronic degrees of freedom, making a fully ab initio dynamics simulation computationally expensive. We demonstrate that the CPA, which removes the need for excited-state nuclear gradients, is well-suited for polaritonic systems because collective light–matter coupling leads to vanishing excited-state forces. Benchmark comparisons between CPA and full evaluation of the excited-state forces show excellent agreement for polariton transport results in model light–matter systems such as polariton group velocities and mean-squared displacements. Ab initio simulations of polariton transport using CPA reproduce key physical trends that are observed in experiments with BODIPY molecules. Our work establishes the CPA as a highly efficient tool for ab initio investigations of transport and energy flow in hybrid light–matter systems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Ab Initio Structures and Energetics of Hydrated Flat and Terrace-Step Surfaces of Forsterite (Mg 2 SiO 4 )

Forsterite (Mg 2 SiO 4 ), a model divalent metal silicate mineral, has been extensively studied in the context of mineral carbonation. Although dissolution is a key step in this process, the mechanisms by which forsterite dissolves under high CO 2 conditions remain poorly understood. Atomistic simulations could aid in exploring these mechanisms, but it is essential first to understand the structures and energetics of the relevant forsterite surfaces. We present an ab initio study of the structure and surface energy at 0 K of the flat $(010), (110), (001), (111), (021), (101)$ and $(120)$ faces of forsterite using the density functional PBE Hamiltonian and a plane-wave basis set. Dry surfaces became stabilized upon hydration through the formation of bonds between surface Mg and O from water, as well as by the formation of hydrogen bonds. According to surface energy values, the stability order of the hydrated forsterite faces was found to be $(120) < (101) < (021) < (111) < (001) < (110) < (010)$. We also investigated the energetics of the terrace-step $(0\bar{41})$ surface as a model site for forsterite dissolution. Among all the facets, the $(0\bar{41})$ surface is the least stable termination in water. Hydration of Mg atoms on the $(0\bar{41})$ surface increases their susceptibility to dissolution. The presence of a step and its hydration destabilizes the terraces, making step retreat more likely than a dissolution front advancing along the [010] direction. This research will support future simulations to investigate forsterite dissolution in water under CO 2 -rich conditions.

PBE Hamiltonian↗
DOE OSTI2023

Determination of the vacancy distribution over Al cation sites in γ-Al 2 O 3

Although gamma-alumina (γ-Al 2 O 3 ) is an extensively used material with wide-ranging applications due to its inherently high surface area and acidity, its atomic structure is still not fully understood. γ-Al 2 O 3 is described as having a spinel-like structure, where the O sublattice has a face-centered cubic (FCC) arrangement and Al cations are placed in the spinel tetrahedral and octahedral interstitial sites. Achieving the correct stoichiometry of Al 2 O 3 , however, requires the introduction of Al vacancies into some of the interstitial sites. Despite the importance of accurately describing the structure of γ-Al 2 O 3 , the distribution of vacancies between tetrahedral and octahedral sites remains unclear, in part because of the usually poor crystalline quality of γ-Al 2 O 3 that has often been used in previous studies. To determine the actual cation distribution in γ-Al 2 O 3 , single-crystalline γ-Al 2 O 3 was investigated using a correlative approach of experimental and simulated selected-area electron diffraction (SAED) and high-resolution electron energy-loss spectroscopy (EELS). Comparison of the reflection intensities in single-crystal SAED to simulated SAED from models with varied vacancy distributions revealed that vacancies exist primarily on tetrahedral sites, contrary to the placement of vacancies on octahedral sites proposed in several common models. Comparison of EELS spectra—acquired with the highest energy resolution reported so far for γ-Al 2 O 3 —with ab initio multiple scattering EELS simulations confirmed the distribution of vacancies on tetrahedral sites. These results enable more accurate modeling of γ-Al 2 O 3 to better predict its properties in existing and future applications.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Evaluation of Density-Functional Tight-Binding Methods for Simulation of Protic Molecular Ion Pairs

In this work, we benchmark the accuracy of the density-functional tight-binding (DFTB) method, namely the long-range corrected second-order (LC-DFTB2) and third-order (DFTB3) models, for predicting energetics of imidazolium-based ionic liquid (IL) ion pairs. We compare the DFTB models against popular density functionals such as LC-ωPBE and B3LYP, using ab initio domain-based local pair-natural orbital coupled cluster (DLPNO-CC) energies as reference. Calculations were carried out in the gas phase, as well as in aqueous solution using implicit solvent methods. We find that the LC-DFTB2 model shows excellent performance in the gas phase and agrees well with reference energies in implicit solvent, often outperforming DFTB3 predictions for complexation energetics. Our study identifies a range of opportunities for use of the LC-DFTB method and quantifies its sensitivity to protonation states and the types of chemical interactions between ion pairs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A numerical study of the meso-structure variability in the compaction process of prepreg platelet molded composites

Compaction deformations in a thermoplastic composite system molded from chopped prepreg platelets were analyzed to obtain statistical distributions of local distortions that define the final consolidated meso-structure. This study provides an insight into and allows quantification of the intrinsic geometric variability of the composite meso-structure that controls the variability of the effective composite mechanical properties. A two-phase viscoelastic finite element model was utilized to treat the behavior of molten prepreg platelets, which were assumed to be incompressible and inextensible in the fiber direction during processing. A two-step simulation procedure with discretely modeled platelets and platelet-to-platelet contacts is proposed. The analysis begins with a drop simulation of the uncontrolled material deposition followed by a 3D finite element analysis of the preform compaction and bulk material flow. The proposed model provides a method for generating a composite meso-structure ab initio starting from a statistical sampling of the initial conditions for platelet deposition. The predicted platelet thickness distribution, intra-platelet fiber waviness and out-of-plane platelet undulations were found to be in good agreement with experimental measurements. An estimate of the volume of resin pockets was inferred from the compaction simulation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Ab initio benchmarks of neutrinoless double- β decay in light nuclei with a chiral Hamiltonian

Here, we report ab initio benchmark calculations of nuclear matrix elements (NMEs) for neutrinoless double-β (0νββ) decays in light nuclei with mass numbers ranging from A = 6 to A = 22. We use the transition operator derived from light-Majorana neutrino exchange and evaluate the NME with three different methods: two variants of in-medium similarity renormalization group (IMSRG) and importance-truncated no-core shell model (IT-NCSM). The same two plus three nucleon interaction from chiral effective field theory is employed, and both isospin-conserving (ΔT = 0) and isospin-changing (ΔT = 2) transitions are studied. We compare our resulting ground-state energies and NMEs to those of recent ab initio no-core shell model and coupled-cluster calculations, also with the same inputs. We show that the NMEs of ΔT = 0 transitions are in good agreement among all calculations, at the level of 10%. For ΔT = 2, relative deviations are more significant in some nuclei. The comparison with the exact IT-NCSM result allows us to analyze these cases in detail, and indicates the next steps toward improving the IMSRG-based approaches. The present study clearly demonstrates the power of consistent cross checks that are made possible by ab initio methodology. This capability is crucial for providing meaningful many-body uncertainties in the NMEs for the 0νββ decays in heavier candidate nuclei, where quasiexact benchmarks are not available.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Protein–Ligand Binding Free-Energy Calculations with ARROW–A Purely First-Principles Parameterized Polarizable Force Field

Protein–ligand binding free-energy calculations using molecular dynamics (MD) simulations have emerged as a powerful tool for in silico drug design. Here, we present results obtained with the ARROW force field (FF)–a multipolar polarizable and physics-based model with all parameters fitted entirely to high-level ab initio quantum mechanical (QM) calculations. ARROW has already proven its ability to determine solvation free energy of arbitrary neutral compounds with unprecedented accuracy. The ARROW FF parameterization is now extended to include coverage of all amino acids including charged groups, allowing molecular simulations of a series of protein–ligand systems and prediction of their relative binding free energies. We ensure adequate sampling by applying a novel technique that is based on coupling the Hamiltonian Replica exchange (HREX) with a conformation reservoir generated via potential softening and nonequilibrium MD. ARROW provides predictions with near chemical accuracy (mean absolute error of ~0.5 kcal/mol) for two of the three protein systems studied here (MCL1 and Thrombin). The third protein system (CDK2) reveals the difficulty in accurately describing dimer interaction energies involving polar and charged species. Overall, for all of the three protein systems studied here, ARROW FF predicts relative binding free energies of ligands with a similar accuracy level as leading nonpolarizable force fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Off-Equilibrium Reactivity of Boron-Enriched Metal Diboride Surfaces in Electroreduction Conditions

Boron-based materials, featuring B-dependent reactivity and diverse phases, are emerging as promising catalyst systems. However, the catalytic mechanism on many borides remains poorly understood due to complex surface reconstructions under reaction conditions. Here, we investigate the MoB 2 surface in conditions of hydrogen evolution reaction in acidic media, using grand canonical global optimization, grand canonical density functional theory, ab initio molecular dynamics, free energy surface sampling, and an analytical model for electrochemical barrier evaluation. We propose a boron-enrichment strategy to tune the surface reactivity of the hexagonal face of MoB 2 . We reveal the dynamic nature of the B-enriched surface under H coverage and kinetic trapping of the system in the metastable regime with an extensive examination of the deactivation pathways. The metastable center B site on B-enriched surfaces, featuring buckled-up configuration and a usual relaxation effect, is found to be highly active toward HER via the Volmer–Heyrovsky mechanism. In conclusion, this work demonstrates how off-equilibrium behaviors can arise from the interplay between adsorbate coverage and surface reconstruction on a seemingly simple surface, and we present a theoretical framework and computational workflows to address these behaviors, along with other realistic complexities, in kinetics simulations.

Adsorption↗
DOE OSTI2024

Anomalous Interlayer Exciton Diffusion in WS 2 /WSe 2 Moiré Heterostructure

Stacking van der Waals crystals allows for the on-demand creation of a periodic potential landscape to tailor the transport of quasiparticle excitations. We investigate the diffusion of photoexcited electron-hole pairs, or excitons, at the interface of WS 2 /WSe 2 van der Waals heterostructure over a wide range of temperatures. We observe the appearance of distinct interlayer excitons for parallel and antiparallel stacking and track their diffusion through spatially and temporally resolved photoluminescence spectroscopy from 30 to 250 K. While the measured exciton diffusivity decreases with temperature, it surprisingly plateaus below 90 K. Our observations cannot be explained by classical models like hopping in the moiré potential. A combination of ab initio theory and molecular dynamics simulations suggests that low-energy phonons arising from the mismatched lattices of moiré heterostructures, also known as phasons, play a key role in describing and understanding this anomalous behavior of exciton diffusion. Our observations indicate that the moiré potential landscape is dynamic down to very low temperatures and that the phason modes can enable efficient transport of energy in the form of excitons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Density of states prediction for materials discovery via contrastive learning from probabilistic embeddings

Abstract Machine learning for materials discovery has largely focused on predicting an individual scalar rather than multiple related properties, where spectral properties are an important example. Fundamental spectral properties include the phonon density of states (phDOS) and the electronic density of states (eDOS), which individually or collectively are the origins of a breadth of materials observables and functions. Building upon the success of graph attention networks for encoding crystalline materials, we introduce a probabilistic embedding generator specifically tailored to the prediction of spectral properties. Coupled with supervised contrastive learning, our materials-to-spectrum (Mat2Spec) model outperforms state-of-the-art methods for predicting ab initio phDOS and eDOS for crystalline materials. We demonstrate Mat2Spec’s ability to identify eDOS gaps below the Fermi energy, validating predictions with ab initio calculations and thereby discovering candidate thermoelectrics and transparent conductors. Mat2Spec is an exemplar framework for predicting spectral properties of materials via strategically incorporated machine learning techniques.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

The O K -2 V spectrum of CO: the influence of the second core-hole

Using synchrotron radiation in the tender X-ray regime, a photoelectron spectrum showing the formation of single site double-core-hole pre-edge states, involving the K shell of the O atom in CO, has been recorded by means of high-resolution electron spectroscopy. The experimentally observed structures have been simulated, interpreted and assigned, employing state-of-the-art ab initio quantum chemical calculations, on the basis of a theoretical model, accounting for their so-called direct or conjugate character. Features appearing above the double ionization threshold have been reproduced by taking into account the strong mixing between multi-excited and continuum states. The shift of the σ* resonance below the double ionization threshold, in combination with the non-negligible contributions of multi-excited configurations in the final states reached, gives rise to a series of avoided crossings between the different potential energy curves.

74 ATOMIC AND MOLECULAR PHYSICS↗