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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Synergistic Density Functional Theory and Molecular Dynamics Approach to Elucidate PNIPAM–Water Interaction Mechanisms

This study employs Density Functional Theory (DFT) and Molecular Dynamics (MD) simulations to investigate interactions between water molecules and Poly(N-isopropylacrylamide) (PNIPAM). DFT reveals preferential water binding sites, with enhanced binding energy observed in the linker zone. Quantum Theory of Atoms in Molecules (QTAIM) and electron localization function (ELF) analyses highlight the roles of hydrogen bonding and steric hindrance. MD simulations unveil temperature-dependent hydration dynamics, with structural transitions marked by changes in the radius of gyration (Rg) and the radial distribution function (RDF), aligning with DFT findings. Our work goes beyond prior studies by combining a DFT, QTAIM and MD simulations approach across different PNIPAM monomer-to-30mer structures. It introduces a systematic quantification of pseudo-saturation thresholds and explores water clustering dynamics with structural specificity, which have not been previously reported in the literature. These novel insights establish a more complete molecular-level picture of PNIPAM hydration behavior and temperature responsiveness, emphasizing the importance of amide hydrogen and carbonyl oxygen sites in hydrogen bonding, which weakens above the lower critical solution temperature (LCST), resulting in increased hydrophobicity and paving the way for understanding water sorption mechanisms, offering guidance for future applications such as dehumidification and atmospheric water harvesting.

08 HYDROGEN↗
DOE OSTI2023

Multiple redox mechanisms for water-gas shift reaction on Fe 3 O 4 (1 1 1) surface: A density functional theory and mean-field microkinetic modeling study

In this work, we investigated redox mechanisms for the high temperature (HT) water–gas shift reaction (WGSR) on the Fe 3 O 4 (1 1 1) surface using density functional theory (DFT) calculations and mean-field microkinetic modeling (MKM). The redox pathways branched into three Langmuir-Hinshelwood processes (LH1, LH2 and LH3) and one Mars-van-Krevelen (MVK) process (in the presence of oxygen vacancy) from multidentate binding of CO and CO 2 over four available reactive sites (Fe oct2 , Fe tet1 , Fe bridge, and O1). We found that the LH1 and LH2 processes have CO adsorption at a single iron site (Fe oct2 or Fe tet1 ), while the LH3 and MVK processes have stronger chemisorption of CO or CO 2 by both the Fe oct2 site and the O 1 site. From the mechanistic study of these reaction path, we recognized that availability of O 1 sites was key to proceed to either CO oxidation by the single site (LH1, LH2) or by the dual site (LH3, MVK). We observed that the reaction energetics were significantly different in the CO oxidation steps, where the single or dual site results in markedly different apparent activation energy (73–281 kJ/mol) and reaction rates (10 -3 –10 -10 mol∙m -2 ∙s -1 ) among the four reaction mechanisms. The utilization of mean field MKM with DFT reaction energetics helps explain the experimental debates for the catalytic reaction details as well as providing a possible direction to engineer the catalyst with higher activity.

42 ENGINEERING↗
DOE OSTI2024

Ni and Co Incorporation in Forsterite: A Density Functional Theory Study with Hubbard Correction

Ni and Co are critical elements for the world economy and modern technologies. Mafic and ultramafic deposits represent low-grade yet abundant alternatives to traditional Ni and Co ores. Here, in this work, density functional theory (DFT) with the Hubbard U correction (DFT+U) was used to simulate the incorporation of Ni and Co in forsterite (Mg 2 SiO 4 ), the Mg endmember of olivine, a common mineral in mafic and ultramafic rocks. Hubbard U terms for Ni and Co were parametrized using a series of oxide, hydroxide, carbonate, silicate, and sulfide minerals relevant to extraction and recovery of Ni and Co from mafic and ultramafic deposits. Electronic, energetic, magnetic, and structural properties were considered in the parametrization. For each of Ni and Co, an effective Hubbard correction (U eff ) value that optimized agreement with either experimental data or a hybrid exchange-correlation functional for all of the minerals considered is reported. DFT+U ab initio molecular dynamics (AIMD) simulations of Ni and Co incorporated into the M1 and M2 octahedral sites of forsterite were then performed. Ni and Co substitution in the M1 site was more energetically favorable than substitution in the M2 site, in agreement with published partition coefficients. AIMD trajectories were used to compute extended X-ray absorption fine structure (EXAFS) spectra of Ni in the M1 and M2 sites for direct fitting to a published experimental spectrum of Ni in a natural San Carlos olivine sample. The results of the fit indicated that ordering of Ni in the M1 site was not as strong at the low Ni concentrations relevant to mafic and ultramafic silicate minerals as that at the higher concentrations of the Ni-Mg olivine solid solutions studied to date.

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

Impact of tensor couplings with scalar mixing on covariant energy density functionals

The recent pioneering campaigns conducted by the Lead Radius Experiment (PREX) and the Calcium Radius Experiment (CREX) Collaborations have uncovered major deficiencies in the theoretical description of some fundamental properties of atomic nuclei. Following a recent refinement to the isovector sector of covariant energy density functionals we present here additional improvements to the functional by including both tensor couplings and an isoscalar-isovector mixing term in the scalar sector. Motivated by the distinct surface properties of calcium and lead, we expect that the tensor terms that generate derivative couplings will help break the linear correlation between the neutron skin thickness of these two nuclei. Moreover, the addition of these new terms mitigates most of the problems identified by Reed et al. in describing the properties of both finite nuclei and neutron stars. While significant progress has been made in reconciling the PREX-CREX results without compromising other observables, the final resolution awaits the completion of a proper calibration for this new class of functionals. As a result, we expect that powerful reduced basis methods used recently to create efficient emulators will be essential to accomplish this task.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Recent progress in global optimizations of covariant energy density functionals

The recent progress on global optimizations of covariant energy den­sity functionals (CEDFs) and global calculations of binding energies within the covariant density functional theory (CDFT) has been analyzed and reviewed. Recently developed anchor-based optimization approach of Ref. [1] allows global optimizations of CEDFs at a reasonable numerical cost. Moreover, it permits such optimizations in a very large fermionic basis with a proper extrap­olation to an infinite one. This allows to accurately estimate global calculation errors due to use of truncated fermionic basis and neglect of some contributions to binding energies (such as total electron binding energy).

Afanasjev, A. V. [Mississippi State University, MS↗
DOE OSTI2024

Understanding the effect of density functional choice and van der Waals treatment on predicting the binding configuration, loading, and stability of amine-grafted metal organic frameworks

Metal organic frameworks (MOFs) are crystalline, three-dimensional structures with high surface areas and tunable porosities. Made from metal nodes connected by organic linkers, the exact properties of a given MOF are determined by node and linker choice. MOFs hold promise for numerous applications, including gas capture and storage. M2(4,4′-dioxidobiphenyl-3,3′-dicarboxylate)—henceforth simply M2(dobpdc), with M = Mg, Mn, Fe, Co, Ni, Cu, or Zn—is regarded as one of the most promising structures for CO2 capture applications. Further modification of the MOF with diamines or tetramines can significantly boost gas species selectivity, a necessity for the ultra-dilute CO2 concentrations in the direct-air capture of CO2. There are countless potential diamines and tetramines, paving the way for a vast number of potential sorbents to be probed for CO2 adsorption properties. The number of amines and their configuration in the MOF pore are key drivers of CO2 adsorption capacity and kinetics, and so a validation of computational prediction of these quantities is required to suitably use computational methods in the discovery and screening of amine-functionalized sorbents. In this work, we study the predictive accuracy of density functional theory and related calculations on amine loading and configuration for one diamine and two tetramines. In particular, we explore the Perdew–Burke–Ernzerhof (PBE) functional and its formulation for solids (PBEsol) with and without the Grimme-D2 and Grimme-D3 pairwise corrections (PBE+D2/3 and PBEsol+D2/3), two revised PBE functionals with the Grimme-D2 and Grimme-D3 pairwise corrections (RPBE+D2/3 and revPBE+D2/3), and the nonlocal van der Waals correlation (vdW-DF2) functional. We also investigate a universal graph deep learning interatomic potential’s (M3GNet) predictive accuracy for loading and configuration. These results allow us to identify a useful screening procedure for configuration prediction that has a coarse component for quick evaluation and a higher accuracy component for detailed analysis. Our general observation is that the neural network-based potential can be used as a high-level and rapid screening tool, whereas PBEsol+D3 gives a completely qualitatively predictive picture across all systems studied, and can thus be used for high accuracy motif predictions. We close by briefly exploring the predictions of relative thermal stability for the different functionals and dispersion corrections.

Chemistry↗
DOE OSTI2022

Molecular interactions from the density functional theory for chemical reactivity: Interaction chemical potential, hardness, and reactivity principles

In the first paper of this series, the authors derived an expression for the interaction energy between two reagents in terms of the chemical reactivity indicators that can be derived from density functional perturbation theory. While negative interaction energies can explain reactivity, reactivity is often more simply explained using the “|dμ| big is good” rule or the maximum hardness principle. Expressions for the change in chemical potential (μ) and hardness when two reagents interact are derived. A partial justification for the maximum hardness principle is that the terms that appear in the interaction energy expression often reappear in the expression for the interaction hardness, but with opposite sign.

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

On the Sensitivity to Density-Functional Approximations for CO Binding Energies of Single-Atom Catalysts in Nitrogen-Doped Graphene

Density functional theory (DFT) methods are the working horse in screening new catalytic materials. They are widely used to predict trends in binding energies, which are then used to compare the activity of different materials. Here, the binding strength of CO is an important descriptor to the CO 2 reduction catalytic activity of the single transition metal atoms embedded on nitrogen-doped graphene (TM/NG). In this work, however, we show that CO binding strengths in different TM/NG has very different sensitivity to DFT methods. Specifically, Fe/NG CO binding energy changes dramatically with the percentage of exact exchange in the functional; Co/NG does less so, while Ni/NG nearly has no change. Such varying behaviors is a direct result of different local spin configurations, similar to the performance of DFT methods for metal porphyrin complexes. Therefore, caution should be exercised when using DFT binding energies for quantitative predictions in TM/NG single atom catalysis.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Time-dependent probability density function analysis of H-mode transitions

Abstract The first application of time-dependent probability density function (PDF) analysis to the L-H transition in fusion plasmas is presented. PDFs are constructed using Doppler Backscattering data of perpendicular fluctuation velocity, , and turbulence from the edge region of the DIII-D tokamak. These raw time-series data are sliced into millisecond-long sliding time-windows to create PDFs. During the transition, the PDFs develop strong right tails, indicative of turbulence-suppressing localised flows in the plasma edge; such features and other subtle behaviours are explored using novel information geometry techniques. This letter examines the applicability of these techniques to predict L-H transitions and investigate predator-prey self-regulation theories between turbulence and perpendicular velocity.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Connecting relativistic density functional theory to microscopic calculations

The development of systematic effective field theories (EFTs) for nuclear forces and advances in solving the nuclear many-body problem have greatly improved our understanding of dense nuclear matter and the structure of finite nuclei. For global nuclear calculations, density functional theories (DFTs) have been developed to reduce the complexity and computational cost required in describing nuclear systems. However, DFT often makes approximations and assumptions about terms included in the functional, which may introduce systematic uncertainties compared to microscopic calculations using EFTs. In this work, we investigate possible avenues of improving nuclear DFT using nonlinear relativistic mean-field (RMF) theory. We explore the impact of RMF model extensions by fitting the nonlinear RMF model to predictions of nuclear matter and selected closed-shell nuclei using four successful chiral EFT Hamiltonians. We find that these model extensions are impactful and important in capturing the physics present within chiral Hamiltonians, particularly for charge radii and neutron skins of closed-shell nuclei. However, there are additional effects that are not captured within the RMF model, particularly within the isoscalar sector of RMF theory. Additional model extensions and the reliability of the nonlinear RMF model are discussed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

Predicting magnetic properties of single-molecule magnets from self-interaction-free density-functional theory (Final Report)

In this project we investigated electronic structure of an intermediate-sized copper-based molecule and magnetic and hyperfine properties of several small non-magnetic and magnetic molecules including transition-metal elements by applying self-interaction corrections to density functional theory (DFT). In a sufficient number of cases, DFT-calculated electronic structure and magnetic properties of single-molecule magnets qualitatively differ from corresponding experimental data. This is partly due to self-interacting electrons within the DFT formalism. Recently, an efficient method to correct the self-interactions was proposed, i.e., Fermi-Lowdin prbital (FLO) based self-interaction corrected (SIC) methodology, within DFT. Henceforth, this method is referred to as FLO-SIC method which exists in FLOSIC code. We used this FLO-SIC method for our studies of electronic structure and magnetic and hyperfine properties of small magnetic molecules and non-magnetic molecules. Our study will provide insight into predictions of magnetic properties of single-molecule magnets where self-interaction corrections play a critical role. There are two components of this project. In the first work, we studied the electronic structure of a planar mononuclear Cu-based molecule in two oxidation states, using DFT with the FLO-SIC method. We chose this system because it is small enough and it includes a transition metal element. We found that the standard FLO-SIC method takes too much compute time even for the small transition-metal molecule and so we slightly modified the method in order to expedite the process. In the dianionic state, we found that the FLO-SIC spin density agrees quantitatively with accurate quantum chemistry methods, while DFT spin density without self-interaction corrections are severely deviated from the quantum chemistry methods. We also showed that the energy gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the dianionic state is larger than that of the monoanionic state. This result is consistent with experimental data. In the second work, we investigated how the interaction between the electron spin and nuclear spin is affected by electron self-interactions within small non-magnetic and magnetic molecules. Such an interaction is called hyperfine interaction. For molecules without significant orbital angular momentum, the hyperfine interaction consists of Fermi contact and dipolar interaction terms. Since the Fermi contact term depends on electron spin density at the nuclear site, it would be highly affected by self-interaction corrections. Therefore, we calculated the hyperfine interaction for the small molecules using DFT with the slightly modified expedited FLO-SIC method which was obtained in the first work, and compared the results to experimental data and DFT calculations without self-interaction corrections. We found significant improvement of the Fermi contact term computed using the FLO-SIC method for small magnetic molecules. Overall, the first and second work provided positive outlook of application of the FLO-SIC method to magnetic molecules and systems including transition-metal elements.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Instability of Rock-Salt Cubic NbN in Density Functional Calculations

All-nitride semiconductor/superconductor heterojunctions utilizing cubic niobium nitride (NbN) are a promising approach to superconducting quantum circuits for next-generation quantum-information systems. However, there are fundamental open questions on the atomic structure of NbN. In calculations with several levels of density functional theory (DFT), we find that the cubic rocksalt structure NbN (Fm-3m, 225) is energetically very unstable against the ground state hexagonal NbN in a tungsten carbide (P-6m2, 187) type lattice. To better understand the appearance of a cubic phase in numerous experiments, we perform a DFT study on possible NbN structures, determining the energy ordering between different polymorphs from databases and structure prediction. We perform supercell calculations of disordered NbN, finding that the rocksalt structure is dynamically unstable and relaxes to a lower energy monoclinic phase (C2/m, 12), which retains an approximate average cubic symmetry. However, the associated energy gain is not substantial enough for a plausible explanation for cubic NbN. We further investigate the role of external factors such as in-plane strain during epitaxial growth as well as the presence of off-stoichiometry and impurity doping on the energy ordering.

CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SU↗
DOE OSTI2025

Vacancy-Dependent Diffusion Mechanism in Oxygen-Defective SrFeO 3 Perovskite Materials: First-Principles Density Functional Theory and Experimental Approach

Understanding oxygen diffusion at the atomic scale in SrFeO 3−δ perovskites is crucial for developing oxygen storage materials with optimal performance. Such materials are required to have high stability, corrosion resistance, and acceptable oxygen storage capacity at moderate operating temperatures and pressures. Here, in this study, we used first-principles density functional theory and thermogravimetric analysis to study the vacancy-dependent oxygen diffusion in oxygen-deficient SrFeO 3−δ (δ = 0, 0.065, 0.125, 0.25, 0.5) perovskites. The electronic structures, including the partial- and spin-resolved density of states, for different SrFeO 3−δ phases were calculated and compared with available experimental and theoretical results. By mapping the migration pathways, we investigated diffusion mechanisms and calculated the energy barriers for oxygen diffusion in cubic, orthorhombic, and brownmillerite phases of SrFeO 3−δ perovskites. Using the calculated energy barriers, we deduced the diffusion time scales and diffusion coefficients within SrFeO 3−δ . A diffusion coefficient on the order of 10 –8 m 2 /s was obtained for SrFeO 2.875 . We experimentally investigated the roles of temperature and oxygen partial pressures on the redox kinetics and deduced the kinetics rate and diffusion density, which agreed well with the calculated values for the density of diffusing oxygen vacancy in the lattice. Our results showed that the energy barrier tends to reduce at higher oxygen concentrations. Our results serve as an important guideline for designing oxygen storage materials with optimal redox kinetics.

chemical looping with oxygen uncoupling (CLOU)↗
DOE OSTI2022

Density functional theory study of formation and diffusion of hydrogen, deuterium, and tritium in Pd-V intermetallic compounds

Permeation of hydrogen isotopes in palladium/vanadium bimetallic membranes is known to deteriorate over time because of Pd-V interdiffusion. Additionally, intermetallic compounds may form in the interdiffusion region. Density functional theory is employed to study how Pd-V compounds may affect the permeation. Three compounds Pd 8 V, alpha-Pd 2 V, and PdV 4 are explored in this study. Formation and migration energies of hydrogen, deuterium, and tritium are calculated and subsequently compared to the data in pure Pd and V metals. The calculations show that both the formation and migration energies in the compounds are higher than in the pure metals. Thus, the permeation of these isotopes in the compounds is lower than in the pure metals. In addition, the least permeable compound is the one near the middle of the composition range, i.e. the alpha-Pd 2 V. The results provide atomistic insight for the permeation reduction in Pd/V membranes as interdiffusion progresses.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Visualisation and outlier detection for probability density function ensembles

Abstract Exploratory data analysis (EDA) for functional data—data objects where observations are entire functions—is a difficult problem that has seen significant attention in recent literature. This surge in interest is motivated by the ubiquitous nature of functional data, which are prevalent in applications across fields such as meteorology, biology, medicine and engineering. Empirical probability density functions (PDFs) can be viewed as constrained functional data objects that must integrate to one and be nonnegative. They show up in contexts such as yearly income distributions, zooplankton size structure in oceanography and in connectivity patterns in the brain, among others. While PDF data are certainly common in modern research, little attention has been given to EDA specifically for PDFs. In this paper, we extend several methods for EDA on functional data for PDFs and compare them on simulated data that exhibit different types of variation, designed to mimic that seen in real‐world applications. We then use our new methods to perform EDA on the breakthrough curves observed in gas transport simulations for underground fracture networks.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

Range‐separated density functional theory using multiresolution analysis and quantum computing

Quantum computers are expected to outperform classical computers for specific problems in quantum chemistry. Such calculations remain expensive, but costs can be lowered through the partition of the molecular system. In the present study, partition was achieved with range-separated density functional theory (RS-DFT). The use of RS-DFT reduces both the basis set size and the active space size dependence of the ground state energy in comparison with the use of wave function theory (WFT) alone. The utilization of pair natural orbitals (PNOs) in place of canonical molecular orbitals (MOs) results in more compact qubit Hamiltonians. To test this strategy, a basis-set independent framework, known as multiresolution analysis (MRA), was employed to generate PNOs. Tests were conducted with the variational quantum eigensolver for a number of molecules. The results show that the proposed approach reduces the number of qubits needed to reach a target energy accuracy.

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

Third-Order Møller–Plesset Theory Made More Useful? The Role of Density Functional Theory Orbitals

The practical utility of Møller–Plesset (MP) perturbation theory is severely constrained by the use of Hartree–Fock (HF) orbitals. It has recently been shown that the use of regularized orbital-optimized MP2 orbitals and scaling of MP3 energy could lead to a significant reduction in MP3 error. In this work, we examine whether density functional theory (DFT)-optimized orbitals can be similarly employed to improve the performance of MP theory at both the MP2 and MP3 levels. We find that the use of DFT orbitals leads to significantly improved performance for prediction of thermochemistry, barrier heights, noncovalent interactions, and dipole moments relative to the standard HF-based MP theory. Indeed, MP3 (with or without scaling) with DFT orbitals is found to surpass the accuracy of coupled-cluster singles and doubles (CCSD) for several data sets. We also found that the results are not particularly functional sensitive in most cases (although range-separated hybrid functionals with low delocalization error perform the best). As such, MP3 based on DFT orbitals thus appears to be an efficient, noniterative O(N 6 ) scaling wave-function approach for single-reference electronic structure computations. Scaled MP2 with DFT orbitals is also found to be quite accurate in many cases, although modern double hybrid functionals are likely to be considerably more accurate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗