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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Molecular dynamics simulations for glass transition temperature predictions of polyhydroxyalkanoate biopolymers

Polyhydroxyalkanoates (PHAs) represent an emerging class of biosynthetic and biodegradable polyesters that exhibit considerable potential to replace petroleum-based plastics towards a sustainable future. Despite the promise, general structure–property mappings within this class of polymers remain largely unexplored. An efficient exploration of this vast chemical space calls for the development and validation of predictive methods for accurate estimation of a diverse range of properties for PHA-based polymers. Towards this aim, we present and validate in this work the results of our molecular dynamics (MD) simulation based approach aimed at predicting glass transition temperatures (T g ) of PHA-based polymers. Since generally available and widely used polymer forcefields exhibit a relatively poor performance for T g predictions, we have developed a new forcefield by modifying the polymer consistent force field (PCFF) via refining a selected set of torsion potentials of the polymer backbone using accurate density functional theory (DFT) computations. After carefully assessing the dependence of critical simulation parameters, such as, polymer chain length, number of polymer chains, supercell size, and thermal quenching rate used in the simulation, the applicability and transferability of the modified PCFF (mPCFF) is demonstrated by directly comparing the computed T g predictions of various polymers with different chemistries, polymer side chain lengths and functional groups forming the polymer side chains against the respective experimentally measured values. Furthermore, the transport properties such as self-diffusion coefficient and viscosity are computationally determined and their well-known correlation with the target properties is demonstrated. Lastly, we have employed the developed approach to predict T g values for a number of yet-to-be-synthesized PHA-based polymers with a diverse set of functional groups in the polymer side chains. The results are further rationalized by correlating the predicted T g values with the inter-chain H-bond formation tendencies of the different side chain functional groups. This work represents an important first step towards computationally guided design of PHA-based functional polymers and opens up new directions for a systematic investigation of composition- and configuration-dependent structure–property relationships in more complex binary and ternary copolymer systems.

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

Variational quantum solver employing the PDS energy functional

In our previous work (J. Chem. Phys. 2020, 153, 201102),we reported a new class of quantum algorithms that are based on the quantum computation of the connected moment expansion to find the ground and excited state energies. In particular, the Peeters-Devreese-Soldatov (PDS) formulation is found variational and bearing the potential for further combining with the existing variational quantum infrastructure. Following this direction, here we propose a variational quantum solver employing the PDS energy gradient. In comparison with the usual variational quantum eigensolver (VQE) and the original static PDS approach, the proposed variational quantum solver offers an effective approach to achieve high ac-curacy at finding the ground state and its energy through the rotation of the trial wave function of modest quality guided by the low order PDS energy gradients, thus improves the ac-curacy and efficiency of the quantum simulation. We demonstrate the performance of the proposed variational quantum solver for toy models, H2molecule, and strongly correlated planar H4system in some challenging situations. In all the case studies, the proposed variational quantum approach out-performs the usual VQE and static PDS calculations even at the lowest order.

Peng, Bo↗
DOE OSTI2022

Uncertainty Quantification in High-Low Dynamic System Coupling using RAVEN and TRANSFORM

This work demonstrates new functionality and applications stemming from the development of high-fidelity to low-fidelity (high-low) coupling for system simulations and to further explore the capabilities of the Risk Analysis Virtual Environment (RAVEN) in the performance of uncertainty quantification in this kind of high-low coupled system models. The work builds from previous work on high-low coupling that utilized COBRA-TF (CTF), the high-fidelity subchannel analysis code, with a low fidelity model built in ORNL’s TRANSFORM, the system analysis code, utilizing the Functional Mock-Up Interface (FMI). Steady-state and transient analysis examples using the high/low coupled models generated from CTF and TRANSFORM/FMI are investigated. The workflows for both steady-state and transient coupled simulations are described. A steady-state parameter sweep and uncertainty analysis of the primary flow rates and reactor power are demonstrated. Likewise, a transient pump trip and power ramp sensitivity studies are also demonstrated. This work elucidates some of the potential benefits and future needs of using RAVEN for high/low system coupling analysis of energy systems. It also shows some of the difficulties that can be encountered in coupling system simulations.

Williams, Wesley↗
DOE OSTI2025

Achieving designed texture and flows in bulk active nematics using optimal control theory

Being intrinsically nonequilibrium, active materials can potentially perform functions that would be thermodynamically forbidden in passive materials. However, active systems have diverse local attractors that correspond to distinct dynamical states, many of which exhibit chaotic turbulent-like dynamics and thus cannot perform work or useful functions. Designing such a system to choose a specific dynamical state is a formidable challenge. Motivated by recent advances enabling optogenetic control of experimental active materials, we describe an optimal control theory framework that identifies a spatiotemporal sequence of light-generated activity that drives an active nematic system toward a prescribed dynamical steady state. Active nematics are unstable to spontaneous defect proliferation and chaotic streaming dynamics in the absence of control. We demonstrate that optimal control theory can compute activity fields that redirect the dynamics into a variety of alternative dynamical programs and functions. This includes dynamically reconfiguring between states, selecting and stabilizing emergent behaviors that do not correspond to attractors, and are hence unstable in the uncontrolled system. Furthermore, our results provide a roadmap to leverage optical control methods to rationally design structure, dynamics, and function in a wide variety of active materials.

Complex systems theory↗
DOE OSTI2023

Bubble Relaxation Dynamics in Homopolymer DNA Sequences

Understanding the inherent timescales of large bubbles in DNA is critical to a thorough comprehension of its physicochemical characteristics, as well as their potential role on helix opening and biological function. In this work, we employ the coarse-grained Peyrard–Bishop–Dauxois model of DNA to study relaxation dynamics of large bubbles in homopolymer DNA, using simulations up to the microsecond time scale. By studying energy autocorrelation functions of relatively large bubbles inserted into thermalised DNA molecules, we extract characteristic relaxation times from the equilibration process for both adenine–thymine (AT) and guanine–cytosine (GC) homopolymers. Bubbles of different amplitudes and widths are investigated through extensive statistics and appropriate fittings of their relaxation. Characteristic relaxation times increase with bubble amplitude and width. We show that, within the model, relaxation times are two orders of magnitude longer in GC sequences than in AT sequences. Overall, our results confirm that large bubbles leave a lasting impact on the molecule’s dynamics, for times between 0.5–500 ns depending on the homopolymer type and bubble shape, thus clearly affecting long-time evolutions of the molecule.

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

The Drell-Yan process with pions and polarized nucleons

The Drell-Yan process provides important information on the internal structure of hadrons including transverse momentum dependent parton distribution functions (TMDs). In this work we present calculations for all leading twist structure functions de- scribing the pion induced Drell-Yan process. The non-perturbative input for the TMDs is taken from the light-front constituent quark model, the spectator model, and available parametrizations of TMDs extracted from the experimental data. TMD evolution is implemented at Next-to-Leading Logarithmic precision for the first time for all asymmetries. Our results are compatible with the first experimental information, help to interpret the data from ongoing experiments, and will allow one to quantitatively assess the models in future when more precise data will become available.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Image-based modeling of coupled electro-chemo-mechanical behavior of Li-ion battery cathode using an interface-modified reproducing kernel particle method

Abstract An interface-modified reproducing kernel particle method (IM-RKPM) is introduced in this work to allow for a direct model construction from image pixels of heterogeneous polycrystalline Li-ion battery microstructures. The interface-modified reproducing kernel (IM-RK) approximation is constructed through scaling of a kernel function by a regularized distance function in conjunction with strategic placement of interface node locations. This leads to RK shape functions with either weak or strong discontinuities across material interfaces, suitable for modeling various interface mechanics. With the placement of a triple junction node and distance-based scaling of kernel functions, the resulting IM-RK shape function also possesses proper discontinuities at the triple junctions. This IM-RK approximation effectively remedies the well-known Gibb’s oscillation in the smooth approximation of discontinuities. Different from the conventional meshfree approaches for interface discontinuities, this IM-RK approach is done without additional degrees of freedom associated with the enrichment functions, and it is formulated with the standard procedures in the RK shape function construction. This work focuses on identifying the accuracy and convergence properties of IM-RKPM for modeling the coupled electro-chemo-mechanical system. A linear patch test is formulated and numerically tested for the electro-chemo-mechanical coupled problem with a Butler–Volmer boundary condition representing the physical conditions in Li-ion battery microstructures. This is followed by verification of the optimal rates of convergence of IM-RKPM for solving the coupled problem with higher order solutions. The image-based modeling of Li-ion battery microstructures in the numerical examples demonstrates the applicability of the proposed method to realistic Li-ion battery materials modeling.

25 ENERGY STORAGE↗
DOE OSTI2023

Challenging the Curse of Dimensionality in Multidimensional Numerical Integration by Using a Low-Rank Tensor-Train Format

Numerical integration is a basic step in the implementation of more complex numerical algorithms suitable, for example, to solve ordinary and partial differential equations. The straightforward extension of a one-dimensional integration rule to a multidimensional grid by the tensor product of the spatial directions is deemed to be practically infeasible beyond a relatively small number of dimensions, e.g., three or four. In fact, the computational burden in terms of storage and floating point operations scales exponentially with the number of dimensions. This phenomenon is known as the curse of dimensionality and motivated the development of alternative methods such as the Monte Carlo method. The tensor product approach can be very effective for high-dimensional numerical integration if we can resort to an accurate low-rank tensor-train representation of the integrand function. In this work, we discuss this approach and present numerical evidence showing that it is very competitive with the Monte Carlo method in terms of accuracy and computational costs up to several hundredths of dimensions if the integrand function is regular enough and a sufficiently accurate low-rank approximation is available.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

Perspectives on van der Waals Density Functionals: The Case of TiS 2

The van der Waals interaction is of foundational importance for a wide variety of physical systems. In particular, van der Waals forces lie at the heart of potential device technologies that may be realized from the functional organization of layered two-dimensional (2D) nanomaterials. Furthermore, for intermediate to large-scale applications modeling, van der Waals density functionals have become the de facto choice for first-principles calculations. In particular, the vdW-DF family of functionals have provided a systematic approach to this theoretically challenging problem. While much progress has been made, there remains room for improvement in the microscopic description of vdW forces from these density functionals. In this work, we compute benchmark results for the binding energy and the electronic density response to binding in TiS2 via accurate diffusion quantum Monte Carlo calculations. We compare these benchmark data to results obtained from local, semilocal, and van der Waals functionals. In particular, we gauge the quality of the original vdW-DF/vdW-DF2 functionals, as well as updated variants such as vdW-DF-C09, vdW-DF-optB88, vdW-DF-optB86b, and vdW-DF2-B86R. We find a close relationship between the accuracy of predicted interlayer separation distances and binding energies for TiS 2 , with the vdW-DF-optB88 functional performing very well in terms of both quantities. In general, the more recently developed functionals are systematic improvements over older ones. However, when considering the response of the electron density to binding, we find that local-density approximation (LDA) and PBEsol generally outperform the vdW-DF functionals in describing the interlayer charge accumulation with vdW-DF-C09 variants performing the best overall.

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

A Functional Survey of the Regulatory Landscape of Estrogen Receptor–Positive Breast Cancer Evolution

Abstract Only a handful of somatic alterations have been linked to endocrine therapy resistance in hormone-dependent breast cancer, potentially explaining ∼40% of relapses. If other mechanisms underlie the evolution of hormone-dependent breast cancer under adjuvant therapy is currently unknown. In this work, we employ functional genomics to dissect the contribution of cis-regulatory elements (CRE) to cancer evolution by focusing on 12 megabases of noncoding DNA, including clonal enhancers, gene promoters, and boundaries of topologically associating domains. Parallel epigenetic perturbation (CRISPRi) in vitro reveals context-dependent roles for many of these CREs, with a specific impact on dormancy entrance and endocrine therapy resistance. Profiling of CRE somatic alterations in a unique, longitudinal cohort of patients treated with endocrine therapies identifies a limited set of noncoding changes potentially involved in therapy resistance. Overall, our data uncover how endocrine therapies trigger the emergence of transient features which could ultimately be exploited to hinder the adaptive process. Significance: This study shows that cells adapting to endocrine therapies undergo changes in the usage or regulatory regions. Dormant cells are less vulnerable to regulatory perturbation but gain transient dependencies which can be exploited to decrease the formation of dormant persisters.

Oncology↗
DOE OSTI2025

Working with Bezier Curves as bases for Functional Expansion Tallies

Functional expansion tallies (FETs) are a powerful tool for getting more information per history from Monte Carlo simulations, but in the past they have been constrained to orthogonal bases. Bezier curves, from computer aided design (CAD), could be well suited for FET due to their ability to assume many arbitrary shapes, but are non-orthogonal. Recent development has made non-orthongal FET possible. The convergence of B ´ezier curve FETs in both polynomial order and number of samples is explored. These bases are well suited for representing normal distributions, and opens the door to possible other CAD derived FET bases.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2023

Functionalized Silicon Particles for Enhanced Half- and Full-Cell Cycling of Si-Based Li-Ion Batteries

Vinylene carbonate (VC) and polyethylene oxide (PEO) have been investigated as functional agents that mimic the solid electrolyte interphase (SEI) chemistry of silicon (Si). VC and PEO are known to contribute to the stability of Si-based lithium-ion batteries as an electrolyte additive and as a SEI component, respectively. In this work, covalent surface functionalization was achieved via a facile route, which involves ball-milling the Si particles with sacrificial VC and PEO. Thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy indicate that the additives are strongly bound to Si. In particular, MAS NMR shows Si–R or Si–O–R groups, which confirm functionalization of the Si after milling in VC or PEO. Particle size analysis by dynamic light scattering reveals that the additives facilitate particle size reduction and that the functionalized particles result in more stable dispersions based on zeta potential measurements. Raman mapping of the electrodes fabricated from the VC and PEO-coated active material with a polyacrylic acid (PAA) binder reveals a more homogenous distribution of Si and the carbon conductive additive compared to the electrodes prepared from the neat Si. Furthermore, the VC-milled Si strikingly exhibited the highest capacity in both half- and full-cell configurations, with more than 200 mAh g –1 measured capacity compared to the neat Si in the half-cell format. This is linked to an improved electrode processing based on the Raman and zeta potential measurements as well as a thinner SEI (with more organic components for the functionalized Si relative to the neat Si) based on XPS analysis of the cycled electrodes. In conclusion, the effect of binder was also investigated by comparing PAA with P84 (polyimide type), where an increased capacity is observed in the latter case.

25 ENERGY STORAGE↗
DOE OSTI2022

Li 8 MnO 6 : A Novel Cathode Material with Only Anionic Redox

In Li-excess transition-metal-oxide cathode materials, anionic oxygen redox can offer high capacity and high voltages, although peroxo and superoxo species may cause oxygen loss, poor cycling performance, and capacity fading. Previous work showed that undesirable formation of peroxide and superoxide bonds is controlled to some extent by Mn substitution, and the present work uses density functional calculations to examine the reasons for this by studying the anionic redox mechanism Li 8 MnO 6 . This material is obtained by substituting Mn for Sn in Li 8 SnO 6 or for Zr in Li 8 ZrO 6 , and we also compare to previous work on those materials. The calculations predict that Li 8 MnO 6 is stable at room temperature (with a band gap of 3.19 eV as calculated HSE06 and 1.82 eV as calculated with the less reliable with PBE+U), and they elucidate the chemical and structural effects involved in the inhibition of oxygen release in this cathode. Throughout the whole delithiation process, only O 2- ions are oxidized. The directional Mn-O bonds formed from unfilled 3d orbitals effectively inhibit the formation of O-O bonds, and the layered structure is maintained even after removing 3 Li per Li 8 MnO 6 formula unit. The calculated average voltage for removal of 3 Li is 3.69 V by HSE06, and the corresponding capacity is 389 mAh/g. The high voltage of oxygen anionic redox and the high capacity result in a high energy density of 1436 Wh/kg. The Li-ion diffusion barrier for the dominant interlayer diffusion path along the c-axis is 0.57 eV by PBE+U. Finally, these results help us to understand the oxygen redox mechanism in a new lithium-rich Li 8 MnO 6 cathode material and contribute to the design of high-energy-density lithium-ion-battery cathode materials with favorable electrochemical properties based on anionic oxygen redox.

Li8MnO6↗
DOE OSTI2024

A DFT-based kinetic Monte Carlo simulation of multiphase oxide-metal thin film growth

Functional thin films of nanoscale metal pillars in oxide or nitride matrices known as vertically aligned nanocomposite (VAN) have gained much interest owing to their unique strain-coupled and highly anisotropic properties. So far, the deposition of these films has been explored mostly experimentally. In this work, a density functional theory (DFT)-based kinetic Monte Carlo simulation model using Bortz–Kalos–Lebowitz algorithm was developed to understand the growth of VAN films deposited by pulsed laser technique on mismatching substrates. The model has been parameterized and applied to understand the kinetics of growth thin films consisting of Au pillars in CeO2 matrix deposited on SrTiO3 substrates. The effects of pulsed laser deposition (PLD) conditions including the pulse frequency, deposition flux, and substrate temperature were explored. The simulations indicate that the Au pillar size and shape exhibit significant dependence on the PLD conditions. Namely, increasing the temperature increases the average pillar size and lowers the pillar density, and vice versa. In addition, the simulations revealed that increasing the deposition rate results in lowering the average pillar size and increasing the density. Particularly, the DFT results suggest that Au pillar size can be tuned during the initial growth of the first monolayer due to the significantly low activation barrier. Our analysis showed that the relationship between the average pillar size and pillar density is influenced by the kinetics. Furthermore, autocorrelation analysis showed that pillars self-organize in quasi-ordered patterns at certain windows of the deposition conditions, which is attributed to the complex nature of the chemical interactions in the system, the kinetics, and the deposition parameters.

Physics↗
DOE OSTI2020

Roles for Countercharge in the Voltage Sensor Domain of Ion Channels

Voltage-gated ion channels share a common structure typified by peripheral, voltage sensor domains. Their S4 segments respond to alteration in membrane potential with translocation coupled to ion permeation through a central pore domain. The mechanisms of gating in these channels have been intensely studied using pioneering methods such as measurement of charge displacement across a membrane, sequencing of genes coding for voltage-gated ion channels, and the development of all-atom molecular dynamics simulations using structural information from prokaryotic and eukaryotic channel proteins. One aspect of this work has been the description of the role of conserved negative countercharges in S1, S2, and S3 transmembrane segments to promote sequential salt-bridge formation with positively charged residues in S4 segments. These interactions facilitate S4 translocation through the lipid bilayer. In this review, we describe functional and computational work investigating the role of these countercharges in S4 translocation, voltage sensor domain hydration, and in diseases resulting from countercharge mutations.

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

Coupling of Flavonoid Initiation Sites with Monolignols Studied by Density Functional Theory

Lignin recalcitrance presents a challenge for the development of a bioeconomy that employs lignocellulosic feedstocks. The efficiency of lignin deconstruction is improved by a reduction of molecular weight, and given the discovery that flavones serve as initiation sites in lignin biosynthesis, these molecular weight reductions could potentially be achieved with plant metabolic engineering to over-express flavonoids. Upon increasing the flavonoid content in lignin, the bond strengths and properties of flavonoid-monolignol linkages become increasingly important. To that end, the current work applies density functional theory calculations to elucidate the bond dissociation enthalpies (BDEs) of flavonoid-monolignol linkages, including dimers with oxidized monolignols. Specifically, the dimer bond strengths and monomer hydrogen abstraction energies for the flavonoids tricin, chrysoeriol, luteolin, apigenin, catechin, epicatechin, epigallocatechin, and epigallocatechin gallate are calculated, when coupled to seven natural and engineered monolignols. Results indicate that 4'-O-ß linkage strengths between flavonoids and monolignols are of comparable strength to inter-monolignol ß-O-4 linkages, with average flavonoid-monolignol BDEs of 70.7 kcal/mol relative to ~69.3 kcal/mol in analogous canonical monolignols. Epigallocatechin yielded the lowest 4'-O-ß bond strength of 52.3 kcal/mol when coupled to an oxidized monolignol, while the flavones overall produced lower average BDEs, relative to the flavanols. Substituents at the 3'-C and 5'-C positions on flavonoids affected the dimer linkage strengths to a greater extent than glycosylation or substituents further from the linkage. Erythro and threo stereochemistry across the flavonoid-monolignol linkage library exhibited only small energetic differences and no pronounced correlations. Taken together, the predictions from this work support the concept that higher concentrations of flavonoid initiation sites in lignin may afford linkage properties conducive to more facile lignin depolymerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗