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Results for “dynamic density functional theory”

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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Mechanistic origins of methyl-driven Overhauser DNP

The Overhauser effect in the dynamic nuclear polarization (DNP) of non-conducting solids has drawn much attention due to the potential for efficient high-field DNP as well as a general interest in the underlying principles that enable the Overhauser effect in small molecules. We recently reported the observation of 1 H and 2 H Overhauser effects in H 3 C- or D 3 C-functionalized Blatter radical analogs, which we presumed to be caused by methyl rotation. In this work, we look at the mechanism for methyl-driven Overhauser DNP in greater detail, considering methyl librations and tunneling in addition to classical rotation. Here, we predict the temperature dependence of these mechanisms using density functional theory and spin dynamics simulations. Comparisons with results from ultralow-temperature magic angle spinning-DNP experiments revealed that cross-relaxation at temperatures above 60 K originates from both libration and rotation, while librations dominate at lower temperatures. Due to the zero-point vibrational nature of these motions, they are not quenched by very low temperatures, and methyl-driven Overhauser DNP is expected to increase in efficiency down to 0 K, predominantly due to increases in nuclear relaxation times.

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

Radiative and Nonradiative Recombinations in Organic Radical Emitters: The Effect of Guest–Host Interactions

Radical-carrying organic molecules have received significant attention to bypass the issue related to harvesting triplet excitons in current light-emitting materials. While the computational efforts conducted so far have treated these radical emitters as isolated entities, in actual devices, they are embedded in a host matrix and subject to emitter–host interactions. In this study, by combining molecular dynamics simulations and density functional theory calculations, the impact of the host matrix on the optoelectronic performance of radical emitters is evaluated, taking as a representative example the (4-ncarbazolyl-2,6-dichlorophenyl)bis(2,4,6-trichlorophenyl)-methyl (TTM-3NCz) radical emitter dispersed in a 4,4-bis(carbazol-9-yl)biphenyl (CBP) host. A morphological analysis shows that steric effects around the radical centers, carried by the TTM electron-poor moieties of the emitters, disfavor π–π interactions with the host molecules, which leads to random intermolecular orientations around the TTM moieties. The 3NCz electron-rich moieties of the emitters, however, have much lesser spatial hindrance for intermolecular π–π stacking, which modulates the structural and electronic properties of the emitters in the host matrix. The influence of dynamic and static disorders on the radiative and nonradiative recombination processes is also investigated and it is found that the rates of nonradiative recombination are small, which opens the way to 100% internal quantum efficiency for the doublet-based emission process.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Dynamic aspects of graphene deformation and fracture from approximate density functional theory

Graphene is one of the most intriguing two-dimensional carbon materials. Its mechanical strength and failure are key concerns for materials engineering and applications. Despite the success of fracture mechanics, the mechanism of how pristine materials fail remains an elusive problem. While many theoretical studies based on molecular dynamics using empirical forcefields have tried to address this question, atomic-scale mechanics are not clearly understood. Especially, a widely employed bond-breaking approach based on the critical bond length has not been rigorously tested. Here, utilizing molecular dynamics simulations with density functional based tight binding, we investigate how the failure of the pristine material initiates. The Wiberg bond order (W BO ) to estimate the change of chemical bonds shows a transition from sp 2 (W BO ~ 1.33) to sp 3 (WBO < 1.0) during the deformation. However, it reveals that a single threshold value for either the WBO or bond length is insufficient to decide failure of pristine material without free edges or defects. Instead, collective behaviors of the local atomic group govern the fracture initiation of pristine graphene. Overall, our study provides dynamic mechanical responses based on quantum mechanics, which have not been captured by empirical forcefields, opening opportunities to design properties by precisely coupling the mechanics and quantum mechanics.

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

Computational Investigations of the Reactivity of Metalloporphyrins for Ammonia Oxidation

Density functional theory and molecular dynamics simulations were used to assess the ability of tetraphenylporphyrin (TPP)M complexes (where M = Cr, Mn, Fe, Co, Ni, Mo, Ru, W, and Os) to coordinate and weaken the N-H bonds of ammonia, as well as their reactivity towards N-N bond formation for N 2 generation. Compared to other metalloporphyrins, bis-ammonia complexes (TPP)Mo(NH 3 ) 2 and (TPP)W(NH 3 ) 2 exhibit low and level N-H BDFEs due to a stabilized (TPP)M(NH 3 )(NH) intermediate by multiple metal-ligand bonding. These results resemble those previously obtained for polypyridyl metal complexes, suggesting that broad trends in reactivity towards N-H bond cleavage are more metal-dependent rather than ligand-dependent for a metal in a nitrogen pseudo-octahedral environment. We investigated N-N bond formation via NH 3 nucleophilic attack on M-NH and M-N intermediates, compared to bimolecular coupling of M-NH x intermediates. We evaluated the reactivity of (TPP)Fe(NH 3 ) 2 towards N-N bond formation via a hydrazine pathway, and found amide-amide coupling to form a bridged hydrazido complex to be the most favorable pathway for N-N bond formation. Further investigation of possible N-N bond formation pathways by reaction with NH 3 led us to identify a possible Fe III -•NH species with significant aminyl character that bypasses the nucleophilic attack of NH 3 and that promotes homolytic N-H bond cleavage of ammonia. This reaction forms a Fe-NH 2 moiety and a transient •NH 2 radical that subsequently forms an N-N bond with the Fe-NH 2 moiety to form a (TPP)Fe(NH 3 )(N 2 H 4 ) species. Furthermore, these results indicate the need to evaluate the radical character of imido species and their reactivity towards N-H bond cleavage of ammonia.

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

Molecular Dynamics Simulation of Hygroscopic Aging Effects in Epoxy Polymer

The automobile industry is incorporating more lightweight content in car designs to boost fuel-economy. New structural adhesives are needed to mitigate the corrosion and thermal expansion issues associated with joining dissimilar lightweight materials, but adhesive developers lack a fundamental understanding of the chemistry that occurs in the adhesive as the joint ages. In this study, we developed structural adhesive molecular models and applied classical molecular dynamics simulations and density functional theory calculations to gain molecular insights into the influence of water molecules on the properties of epoxy-based adhesives (DGEBA + Jeffamine (JD230)). The simulations were complemented by experimental synthesis and characterization. Our work underscores the impact of water molecules on the local structure of the epoxy network as well as resulting mechanical properties. Water molecules were mainly coordinated with hydroxyls, primary amines and secondary amines, but also weakly coordinated with ether linkages, which were found most probable to be labile. Simulated stress–strain data indicates that increasing the water content deteriorates the mechanical properties. The Young’s modulus decreased by ~ 30% when the water content increased to 3 wt%. We conclude, this integration of molecular-level chemical insights with mechanical property simulations of the hydrated epoxy system and experimental validation holds the promise to advance lightweight joint technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Insights into the Reactivity of Brookite TiO 2 Nanorods in Liquid Water from Ab Initio Molecular Dynamics Simulations

Brookite TiO 2 , a rare natural polymorph of TiO 2 , has been reported to be an excellent photocatalyst for the production of hydrogen from water and aqueous alcohol solutions, especially when it is reduced and synthesized in the form of nanorods. Here, we investigate the reactivity of stoichiometric and reduced brookite nanorods in liquid water using ab initio molecular dynamics and hybrid density functional theory calculations. Our simulations show a much higher water dissociation fraction on reduced nanorods than on stoichiometric ones, with an accumulation of the resulting bridging hydroxyls (O br H) and terminal hydroxyls (Ti –OH) on different facets of the nanorod. ObrH groups accumulate preferentially on low-energy (210) facets, where they are stabilized by adjacent reduced Ti (Ti 3+ ) sites, while Ti –OH groups prefer to form at the four-fold coordinated Ti atoms on high-energy (010) facets. This hydroxylation pattern also favors the spatial localization of excited holes on the (010) facets. This coupling between water-induced surface chemistry and charge separation underpins the enhanced photocatalytic activity of brookite nanorods, providing useful information for the design of more efficient TiO2-based nanostructures for solar-driven hydrogen evolution.

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

The symmetric quasi-classical model using on-the-fly time-dependent density functional theory within the Tamm–Dancoff approximation

The primary computational challenge when simulating nonadiabatic ab initio molecular dynamics is the unfavourable compute costs of electronic structure calculations with molecular size. Simple electronic structure theories, like time-dependent density functional theory within the Tamm–Dancoff approximation (TDDFT/TDA), alleviate this cost for moderately sized molecular systems simulated on realistic time scales. Although TDDFT/TDA does have some limitations in accuracy, an appealing feature is that, in addition to including electron correlation through the use of a density functional, the cost of calculating analytic nuclear gradients and nonadiabatic coupling vectors is often computationally feasible even for moderately sized basis sets. Here in this work, some of the benefits and limitations of TDDFT/TDA are discussed and analysed with regard to its applicability as a ‘back-end’ electronic structure method for the symmetric quasi-classical Meyer–Miller model (SQC/MM). In order to investigate the benefits and limitations of TDDFT/TDA, SQC/MM is employed to predict and analyse a prototypical example of excited-state hydrogen transfer in gas-phase malonaldehyde. Then, the ring-opening dynamics of selenophene are simulated, which highlight some of the deficiencies of TDDFT/TDA. Additionally, some new algorithms are proposed that speed up the calculation of analytic nuclear gradients and nonadiabatic coupling vectors for a set of excited electronic states.

molecular dynamics↗
DOE OSTI2024

High‐Energy LiNiO 2 Li Metal Batteries Enabled by Hybrid Electrolyte Consisting of Ionic Liquid and Weakly Solvating Fluorinated Ether

Abstract In pursuit of the highest possible energy density, researchers shift their focus to the ultimate anode material, lithium metal (Li 0 ), and high‐capacity cathode materials with high nickel content (Ni > 80%). The combination of these aggressive electrodes presents unprecedented challenges to the electrolyte. Here, we report a hybrid electrolyte consisting of a highly fluorinated ionic liquid and a weakly solvating fluorinated ether, whose hybridization structure enables the reversible operation of a battery chemistry based on Li 0 and LiNiO 2 (Ni = 100%), delivering nearly theoretical capacity of the latter (up to 249 mAh g −1 ) for >300 cycles with retention of 78.6% and in absence of unwanted morphological changes in both electrodes. Extensive characterization assisted by molecular dynamic simulation and density functional theory calculations reveals the function of the fluorinated ether to be far more profound than simple dilution and viscosity reduction. Instead, it induces drastic changes in Li + ‐solvation environment, the consequence of which engenders simultaneous stabilization of electrode/electrolyte and interfacing via formation of respective interfacial chemistries. This study further unlocks fundamental knowledge underneath the prevailing “diluent strategy” that is extensively applied by the electrolyte researchers and opens more design space for the next‐generation electrolytes and interphases for these coveted battery chemistries.

25 ENERGY STORAGE↗
DOE OSTI2022

Single Atoms Anchored in Hexagonal Boron Nitride for Propane Dehydrogenation from First Principles

We report single-atom catalysts embedded in N-doped graphene have attracted great interest recently, but the hexagonal boron nitride (h-BN) is much less explored as a support. Using first principles density function theory and molecular dynamics, here we investigate the stability of Pt, Au, and Ru single atoms anchored at B and N vacancies on h-BN. We find that Pt and Ru single atoms are much more stable than Au on h-BN. We further examine propane dehydrogenation on these single-atom catalysts and find that Pt 1 at the B vacancy in h-BN and Ru 1 at the N vacancy in h-BN show excellent activity for propane dehydrogenation, as evidenced by low energy barriers for both dehydrogenation steps. Our work suggests that Pt and Ru single atoms anchored at vacancy sites in h-BN could be promising for propane dehydrogenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Activation of dislocations in Mg with solute Y

Mg-Y cast alloy shows excellent ductility (elongation to failure > 15%) compared with pure Mg and commercial Mg cast alloys. By monitoring the microstructure evolution during an in situ tensile test of a Mg-2.5 wt%Y alloy, we identify the activation of prismatic slip, which is rare in Mg. Synchrotron X-ray micro-beam Laue diffraction (μ-Laue) and transmission electron microscopy revealed the morphology of prismatic slip bands and individual dislocations. Density functional theory and molecular dynamics calculations indicate that solute Y can significantly reduce the stacking fault energy (SFE) along direction on prismatic plane in Mg lattice and thus facilitate the nucleation of dislocations during deformation. The presence of free dislocations in the Mg lattice can also lead to nucleation of {10–12} twins even under unfavorable geometric conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2025

The total neutron cross section of liquid and solid ammonia

Ammonia is a material of interest for future neutron moderators at high-power sources due to its high hydrogen density, low melting point, and resistance to polymerization in an intense radiation field. Its performance in such applications cannot currently be calculated due to the absence of suitable computer models for the interaction of neutrons with ammonia under relevant conditions. In an effort to develop suitable scattering kernels for computer simulations of moderator performance, we have conducted a series of Density Functional Theory and Molecular Dynamics calculations of the molecular-level thermal properties of ammonia at various temperatures within both the solid and liquid phases. In this paper, we compare computer calculations for the energy-dependent total neutron cross section of ammonia, based on these models, to experimental measurements of those cross sections at temperatures of 221 K, 180 K, and 35 K. The experimental data were collected over an energy range from 0.1 meV to 10 eV using time-of-flight techniques at the Low Energy Neutron Source (LENS) facility at Indiana University. This comparison provides a first validation in the development of thermal scattering libraries for Monte Carlo source design simulations based on liquid and solid ammonia. In conclusion, we also provide some insights into where additional development of tools for creating such models may be needed.

Ammonia↗
DOE OSTI2020

The Role of Cation Coordination in the Electrical and Optical Properties of Amorphous Transparent Conducting Oxides

Amorphous oxide semiconductor materials have demonstrated numerous advantages without compromise of electrical properties as compared to their crystalline counterparts, yet understanding of the fundamental principles allowing this has remained elusive. To study the origins of enhanced optoelectronic properties, we apply high-throughput, combinatorial sputtering, structural and spectral mapping, and computationally intensive ab initio molecular dynamics simulations with density functional theory to a ternary, post-transition metal oxide system, namely, zinc tin oxide. The deposited thin films exhibit a high figure of merit, achieving carrier densities in the range of 1019 to 1020 cm–3 and carrier mobilities up to 35 cm2/Vs. These results highlight the role of local distortions and cation coordination in determining the microscopic origins of carrier generation and transport. In particular, we identify the strong likelihood of Sn undercoordination in both Zn-poor and Zn-rich phases leading to the high carrier concentrations observed. This not only diverges from the still widespread historical indictment of oxygen vacancies controlling carrier population in crystalline oxides but also provides a comprehensive framework to describe the unique structure–property relationships using specific structural and electronic descriptors in disordered phase materials.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS,M↗
DOE OSTI2025

Ion Size Effects on the Thermodynamic, Kinetic, and Mechanical Properties during Ion Exchange in Solid-State Electrolytes

Ion exchange offers a pathway to impose residual compressive stresses to mitigate the electro-chemo-mechanical cracking of solid-state electrolytes such as lithium lanthanum zirconium oxide. This study uses a coupled multiscale framework (integrating density functional theory (DFT), molecular dynamics (MD), and continuum modeling) to examine how exchange ion size influences stress, diffusion, fracture toughness, and electronic properties. Larger isovalent ions (Na + , Ag + , K + ) were exchanged with Li + , with DFT confirming their preference for octahedral 96h sites and a linear relationship between ion size and chemical free expansion coefficient. MD simulations reveal stress and concentration effects on exchange ion diffusivity at elevated temperatures, with Na + and Ag + maintaining favorable mobility while K + showing concentration-dependent clustering. Continuum modeling predicts the range of fracture strength improvements and the required ion exchange concentration profile. It was shown that a 5% surface exchange concentration can induce ∼0.6 GPa of surface compressive stress using Na + and ∼1.0 GPa of surface compressive stress using Ag + . On the other hand, larger ion exchange species may penalize Li + diffusivity by increasing the activation volume and activation energy. Interestingly, Na + has a negligible penalty on Li-ion diffusivity. The room temperature Li + ion diffusivity is reduced by ∼40% with Ag + ion exchange. Electronic band structure analysis shows no size-dependent change in the bandgap, though Ag + introduces localized defect states near the valence band maximum. This study highlights ion size as a key factor in optimizing LLZO properties, offering a framework to improve the solid-state battery performance.

Jagad, Harsh D. [Brown Univ., Providence, RI (Unit↗
DOE OSTI2023

Impact of Hydrogen Bonds on CO 2 Binding in Eutectic Solvents: An Experimental and Computational Study toward Sorbent Design for CO 2 Capture

Choline-based amino acid ionic liquids with anions glycinate, β-alaninate, phenylalaninate, and prolinate were synthesized and mixed with ethylene glycol to form lower-viscosity benign eutectic solvents for CO 2 capture. The highest capacity measured was 0.7 moles of CO 2 per mole of ionic liquid (2 moles CO 2 per kg solvent) for a 1 to 2 mole ratio mixture of choline prolinate to ethylene glycol at 1 bar of CO 2 and 25 °C. Under 5000 ppm of CO 2 , half of this capacity was realized. Here, through a combined study of quantitative 13 C NMR spectroscopy, molecular dynamics simulations and density functional theory calculations, we show that hydrogen bonding in the eutectic solvent prevents proton-transfer between prolinate anions upon CO 2 absorption, which occurs in the absence of ethylene glycol and deactivates binding sites. Blocking this proton transfer leads to a higher binding capacity compared to neat choline prolinate. This work demonstrates the impact of hydrogen bonding on the CO 2 binding mechanism and energetics, as well as physical and thermal properties in eutectic solvents, thus addressing an unmet need and informing future studies on the development of benign sorbents for capturing CO 2 from dilute streams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Atomic-Scale Imaging Reveals Polar-π Interactions in Two-Dimensional Molecular Superlattices

Controlling coassembly of synthetic oligomers into binary superlattices at the atomic level is challenging. Here, we report a strategy for programming polar-π interactions in oligomeric peptoids, a class of sequence-defined peptidomimetics, facilitating the formation of homogeneous two-dimensional (2D) superlattices. N-2-phenylethyl and N-(2-perfluorophenyl)ethyl side chains, similar in size, but with contrasting electrostatic characteristics, were introduced at defined sequence positions to generate favorable dipolar aromatic interactions. The resulting nanosheets exhibit different crystal motifs depending on the side chain interactions: systems containing only one type of aromatic side chain form a parallel V-shaped motif driven by π-π interactions, whereas a combination of both types of aromatic side chains, either within one backbone or through the coassembly of two distinct peptoids, adopt an antiparallel V-shaped superlattice with higher thermal stability, driven by polar-π interactions. Cryogenic transmission electron microscopy directly resolved the packing arrangement of perfluorophenyl and phenyl rings in individual nanosheet superlattices, confirming that intermolecular polar-π interaction dominates the superlattice motifs and increases lattice stability. Molecular dynamics simulations and density functional theory calculations further substantiate the energetic favorability of polar-π interactions over π-π interactions, rationalizing the formation of homogeneous superlattices with enhanced thermal stability. Our discoveries establish a design principle for binary coassembly using sequence-defined oligomers, which enables control over unit cell geometry, lattice stability, and molecular registration through aromatic side chain polarization and sequence control. This ability to program atomic-scale binary superlattices opens new avenues for designing functional 2D soft materials.

Lee, Yen Jea [Lawrence Berkeley National Laborator↗
DOE OSTI2020

99 TcO 4 - removal from legacy defense nuclear waste by an alkaline-stable 2D cationic metal organic framework

Removal of 99 TcO 4 - from legacy defense nuclear tank waste at Savannah River Site is highly desirable for the purpose of nuclear safety and environmental protection, but currently not achievable given the extreme conditions including high alkalinity, high ionic strength, and strong radiation field. Herein, we present a potential solution to this long-term issue by developing a two-dimensional cationic metal organic framework SCU-103, showing ultrahigh stability in alkaline aqueous media and great resistance to both β and γ radiation. More importantly, it is very effective for 99 TcO 4 - separation from aqueous media as demonstrated by fast exchange kinetics, high sorption capacity, and superior selectivity, leading to the successful removal of 99 TcO 4 - from actual Savannah River Site high level tank waste for the first time, to the best of our knowledge. In addition, the uptake mechanism is comprehensively elucidated by molecular dynamics simulation and density functional theory calculation, showing a unique chemical recognition of anions with low charge density.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2022

Identification of a quasi-liquid phase at solid–liquid interface

Abstract An understanding of solid–liquid interfaces is of great importance for fundamental research as well as industrial applications. However, it has been very challenging to directly image solid–liquid interfaces with high resolution, thus their structure and properties are often unknown. Here, we report a quasi-liquid phase between metal (In, Sn) nanoparticle surfaces and an aqueous solution observed using liquid cell transmission electron microscopy. Our real-time high-resolution imaging reveals a thin layer of liquid-like materials at the interfaces with the frequent appearance of small In nanoclusters. Such a quasi-liquid phase serves as an intermediate for the mass transport from the metal nanoparticle to the liquid. Density functional theory-molecular dynamics simulations demonstrate that the positive charges of In ions greatly contribute to the stabilization of the quasi-liquid phase on the metal surface.

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

Solvent oligomerization pathways facilitated by electrolyte additives during solid-electrolyte interphase formation

The solid–electrolyte interphase (SEI) layer formation is known to play an important role in determining the lifetime of lithium-ion batteries. A thin, stable SEI layer is linked to overall improved battery performance and longevity, however, the factors and mechanisms that lead to optimal SEI morphology and composition are not well understood. Inclusion of electrolyte additives (fluoroethylene carbonate, FEC; and vinylene carbonate, VC) is often necessary for improving SEI characteristics. To understand how these electrolyte additives impact SEI formation, we employed molecular dynamics (MD) and density functional theory (DFT) simulations to study the reaction networks and oligomerization pathways, respectively, for three systems containing ethylene carbonate (EC), a lithium ion, and FEC or VC. MD simulations suggest radical oligomerization pathways analogous to traditional oligomerization with nucleophilic alkoxide species via SN1 reaction mechanisms. Both S N 1 and S N 2 mechanisms were studied for all three systems using DFT. Oligomerization reactions were studied with both a standard alkoxide species and a ring-opened EC radical as the nucleophiles and EC, FEC, and VC as the electrophiles. For all cases, FEC and VC exhibited lower free energy barriers and more stable adducts when compared with EC. We conclude that one of the role of additives is to modify the oligomerization process of EC by introducing branching points (FEC) or termination points (VC).

25 ENERGY STORAGE↗