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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 667 records · Page 37
All sourcesNASA NTRSDOE OSTI
NASA NTRS1998

A Synthesis of Fluid Dynamics and Quantum Chemistry for the Design of Nanoelectronics

In 1959, during a famous lecture entitled "There's Plenty of Room at the Bottom", Richard Feynman focused on the startling technical possibilities that would exist at the limit of miniaturization, that being atomically precise devices with dimensions in the nanometer range. A nanometer is both a convenient unit of length for medium to large sized molecules, and the root of the name of the new interdisciplinary field of "nanotechnology". Essentially, "nanoelectronics" denotes the goal of shrinking electronic devices, such as diodes and transistors, as well as integrated circuits of such devices that can perform logical operations, down to dimensions in the range of 100 nanometers. The thirty-year hiatus in the development of nanotechnology can figuratively be seen as a period of waiting for the bottom-up and atomically precise construction skills of synthetic chemistry to meet the top-down reductionist aspirations of device physics. The sub-nanometer domain of nineteenth-century classical chemistry has steadily grown, and state-of-the-art supramolecular chemistry can achieve atomic precision in non-repeating molecular assemblies of the size desired for nanotechnology. For nanoelectronics in particular, a basic understanding of the electron transport properties of molecules must also be developed. Quantum chemistry provides powerful computational methods that can accurately predict the properties of small to medium sized molecules on a desktop workstation, and those of large molecules if one has access to a supercomputer. Of the many properties of a molecule that quantum chemistry routinely predicts, the ability to carry a current is one that had not even been considered until recently. "Currently", there is a controversy over just how to define this key property. Reminiscent of the situation in high-Tc superconductivity, much of the difficulty arises from the different models that are used to simplify the complex electronic structure of real materials. A model-independent approach has been proposed, that sacrifices the plentiful molecular orbitals and Bloch functions of conventional approaches, for a single three-dimensional observable quantity, the electron momentum density Pi(sub rho). This quantity is simply the probability of any electron having momentum rho, multiplied by the total number of electrons in the system (the position of the electron is uncertain). We have explored the utility of this new approach in providing a fundamental understanding of the electron transport properties of molecules that have provi been nominated as candidates for components in the design of nanoelectronics; phenylene-ethynylene oligomers. Some of the molecular systems that have been studied are sketched below.

MacDougall, Preston J.↗
DOE OSTI2024

Molecular origin of viscoelasticity and influence of methylation in mesophase pitch

The viscoelastic and thermomechanical properties of pitches are responsible for their melt-spinning behavior, which is a critical step for manufacturing high-performance pitch-based carbon fibers. Here, we systematically explore the impact of methyl group modifications on the viscoelastic and thermal properties of mesophase pitches. We employ a range of atomistic modeling approaches, including Density Functional Theory (DFT), Density Functional Tight Binding (DFTB), and Classical Molecular Mechanics (MM), to provide detailed insights into the molecular interactions and structural changes. Further, our results revealed the molecular mechanisms that promote layered structures leading to the anisotropic nature of the viscoelastic behavior of mesophase pitch. Furthermore, we propose a modified molecular representation of naphthalene-based mesophase pitch based on the analysis of x-ray diffraction measurements. This study provides fundamental insights into the molecular structures of mesophase pitch and the role of methyl groups controlling its viscosity, which offer valuable insights into mesophase-based carbon fiber production.

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

Helfrich-Hurault elastic instabilities driven by geometrical frustration

Here, the Helfrich-Hurault (HH) elastic instability is a well-known mechanism behind patterns that form as a result of strain upon liquid crystal systems with periodic ground states. In the HH model, layered structures undulate and buckle in response to local, geometric incompatibilities in order to maintain the preferred layer spacing. Classic HH systems include cholesteric liquid crystals under electromagnetic field distortions and smectic liquid crystals under mechanical strains, where both materials are confined between rigid substrates. However, richer phenomena are observed when undulation instabilities occur in the presence of deformable interfaces and variable boundary conditions. Understanding how the HH instability is affected by deformable surfaces is imperative for applying the instability to a broader range of materials. In this review, the HH mechanism is reexamined and special focus is given to how the boundary conditions influence the response of lamellar systems to geometrical frustration. Lamellar liquid crystals confined within a spherical shell geometry are used as the model system. Made possible by the relatively recent advances in microfluidics within the past 15 years, liquid crystal shells are composed entirely of fluid interfaces and have boundary conditions that can be dynamically controlled at will. Past and recent work that exemplifies how topological constraints, molecular anchoring conditions, and boundary curvature can trigger the HH mechanism in liquid crystals with periodic ground states is examined. The review ends by identifying similar phenomena across a wide variety of materials, both biological and synthetic. The fact that the HH mechanism is a generic and often overlooked response of periodic materials to geometrical frustration is highlighted.

42 ENGINEERING↗
DOE OSTI2024

Dynamic population balance in molecular-level simulations of hypersonic flows

This report summarizes the work towards developing stochastic weighted particle methods (SWPM) for future application in hypersonic flows. Extensive changes to Sandia’s direct simulation Monte Carlo (DSMC) solver, SPARTA (Stochastic Particle Real Time Analyzer), were made to enable the necessary particle splitting and reduction capabilities for SWPM. The results from one-dimensional Couette and Fourier flows suggest that SWPM can reproduce the correct transport for a large range of Knudsen numbers with adequate accuracy. The associated velocity and temperature profiles are in good agreement with DSMC. An issue with particle placement during particle number reduction, is identified, to which, a simple but effective solution based on minimizing the center of mass error is proposed. High Mach wheel flows are simulated using the SWPM and DSMC methods. SWPM is capable of providing nearly an order of magnitude increase in efficiency over DSMC while retaining high accuracy.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Differentiating Three-Dimensional Molecular Structures Using Laser-Induced Coulomb Explosion Imaging

Coulomb explosion imaging (CEI) with x-ray free electron lasers has recently been shown to be a powerful method for obtaining detailed structural information of gas-phase planar ring molecules [R. Boll et al., X-ray multiphoton-induced Coulomb explosion images complex single molecules, Nat. Phys. 18, 423 (2022).]. In this Letter, we investigate the potential of CEI driven by a tabletop laser and extend this approach to differentiating three-dimensional structures. We study the static CEI patterns of planar and nonplanar organic molecules that resemble the structures of typical products formed in ring-opening reactions. Here, our results reveal that each molecule exhibits a well-localized and distinctive pattern in three-dimensional fragment-ion momentum space. We find that these patterns yield direct information about the molecular structures and can be qualitatively reproduced using a classical Coulomb explosion simulation. Our findings suggest that laser-induced CEI can serve as a robust method for differentiating molecular structures of organic ring and chain molecules. As such, it holds great promise as a method for following ultrafast structural changes, e.g., during ring-opening reactions, by tracking the motion of individual atoms in pump-probe experiments.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Mixed quantum–classical approach to model non-adiabatic electron–nuclear dynamics: Detailed balance and improved surface hopping method

We develop a density matrix formalism to describe coupled electron–nuclear dynamics. To this end, we introduce an effective Hamiltonian formalism that describes electronic transitions and small (quantum) nuclear fluctuations along a classical trajectory of the nuclei. Using this Hamiltonian, we derive equations of motion for the electronic occupation numbers and for the nuclear coordinates and momenta. We show that, in the limit, when the number of nuclear degrees of freedom coupled to a given electronic transition is sufficiently high (i.e., the strong decoherence limit), the equations of motion for the electronic occupation numbers become Markovian. Furthermore, the transition rates in these (rate) equations are asymmetric with respect to the lower-to-higher energy transitions and vice versa. In thermal equilibrium, such asymmetry corresponds to the detailed balance condition. We also study the equations for the electronic occupations in the non-Markovian regime and develop a surface hopping algorithm based on our formalism. To treat the decoherence effects, we introduce additional “virtual” nuclear wave packets whose interference with the “real” (physical) wave packets leads to the reduction in coupling between the electronic states (i.e., decoherence) as well as to the phase shifts that improve the accuracy of the numerical approach. Remarkably, the same phase shifts lead to the detailed balance condition in the strong decoherence limit.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Light-induced electron spin qubit coherences in the purple bacteria reaction center protein

Photosynthetic reaction center proteins (RCs) provide ideal model systems for studying quantum entanglement between multiple spins, a quantum mechanical phenomenon wherein the properties of the entangled particles become inherently correlated. Following light-generated sequential electron transfer, RCs generate spin-correlated radical pairs (SCRPs), also referred to as entangled spin qubit (radical) pairs (SQPs). Understanding and controlling coherence mechanisms in SCRP/SQPs is important for realizing practical uses of electron spin qubits in quantum sensing applications. The bacterial RC (bRC) provides an experimental system for exploring quantum effects in the SCRP P 865 + Q A − , where P 865 , a special pair of bacteriochlorophylls, is the primary donor, and Q A is the primary quinone acceptor. In this study, we focus on understanding how local molecular environments and isotopic substitution, particularly deuteration, influence spin coherence times (T M ). Using high-frequency electron paramagnetic resonance (EPR) spectroscopy, we observed that the local environment surrounding P 865 and Q A plays a significant role in determining T M . Our findings show that while deuteration led to a modest increase in T M , particularly at low temperatures, but the effect was substantially smaller than predicted by classical nuclear spin diffusion alone. This result is in contrast to our previous study of the photosystem I (PSI) RC, where no increase in T M was observed upon deuteration. Theoretical modeling identified several methyl groups at key distances from the spin centers of both bRC and PSI, and methyl group tunneling at low temperatures has been previously suggested as a mechanism for enhanced spin decoherence. Additionally, our study revealed a strong dependence of spin coherence on the orientation of the external magnetic field, highlighting the influence of the protein microenvironment on spin dynamics. In conclusion, these results offer new insights for optimizing coherence times in quantum system design for quantum information science and sensing applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2016

Evaluation of Methods for Molecular Dynamics Simulation of Ionic Liquid Electric Double Layers

We investigate how systematically increasing the accuracy of various molecular dynamics modeling techniques influences the structure and capacitance of ionic liquid electric double layers (EDLs). The techniques probed concern long-range electrostatic interactions, electrode charging (constant charge versus constant potential conditions), and electrolyte polarizability. Our simulations are performed on a quasi-two-dimensional, or slab-like, model capacitor, which is composed of a polarizable ionic liquid electrolyte, [EMIM][BF4], interfaced between two graphite electrodes. To ensure an accurate representation of EDL differential capacitance, we derive new fluctuation formulas that resolve the differential capacitance as a function of electrode charge or electrode potential. The magnitude of differential capacitance shows sensitivity to different long-range electrostatic summation techniques, while the shape of differential capacitance is affected by charging technique and the polarizability of the electrolyte. For long-range summation techniques, errors in magnitude can be mitigated by employing two-dimensional or corrected three dimensional electrostatic summations, which lead to electric fields that conform to those of a classical electrostatic parallel plate capacitor. With respect to charging, the changes in shape are a result of ions in the Stern layer (i.e. ions at the electrode surface) having a higher electrostatic affinity to constant potential electrodes than to constant charge electrodes. For electrolyte polarizability, shape changes originate from induced dipoles that soften the interaction of Stern layer ions with the electrode. The softening is traced to ion correlations vertical to the electrode surface that induce dipoles that oppose double layer formation. In general, our analysis indicates an accuracy dependent differential capacitance profile that transitions from the characteristic camel shape with coarser representations to a more diffuse profile with finer representations.

Haskins, Justin B.↗
DOE OSTI2025

Breaking the curse of dimensionality: Solving configurational integrals for crystalline solids by tensor networks

Accurately evaluating configurational integrals for dense solids remains a central and difficult challenge in the statistical mechanics of condensed systems. Here, we present a tensor network approach that reformulates the high-dimensional configurational integral for identical-particle crystals into a sequence of computationally efficient summations. We represent the integrand as a high-dimensional tensor and apply tensor-train (TT) decomposition together with a custom TT-cross interpolation. This approach circumvents the need to explicitly construct the full tensor. We introduce tailored rank-1 and rank-2 schemes optimized for sharply peaked Boltzmann probability densities, typical for identical-particle crystals. When applied to the calculation of internal energy and pressure-temperature curves for crystalline Cu and Ar at high (GPa) pressures, as well as the alpha-to-beta phase transition diagram of Sn, our method accurately reproduces molecular dynamics simulation results using tight-binding, machine learning, hierarchical interacting particle–neural network, and modified embedded atom method potentials,all within seconds of computation time.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Sensing ultrashort electronic coherent beating at conical intersections by single-electron pulses

In a theoretical study, we present an ultrafast technique for probing time-dependent molecular charge densities. An ultrafast optical pump first brings the molecule into an electronic nonstationary state. This is followed by coherent inelastic scattering of a broadband single-electron probe pulse with a variable delay T, which is detected spectrally. The technique is applied to reveal phase-sensitive background-free coherent electron beating in the conical intersection passage in uracil and reveals the otherwise elusive coherent beating of strongly coupled electrons and nuclei.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Enhancing the formation of ionic defects to study the ice Ih/XI transition with molecular dynamics simulations

Ice Ih, the common form of ice in the biosphere, contains proton disorder. Its proton-ordered counterpart, ice XI, is thermodynamically stable below 72 K. However, the formation of ice XI is kinetically hindered, and experimentally it is obtained by doping with KOH. Doping creates ionic defects that promote the migration of protons and the associated change in proton configuration. In this article, we mimic the effect of doping with a bias potential that enhances the formation of ionic defects in molecular dynamics simulations. The recombination of the ions thus formed proceeds through fast migration of the hydroxide along hydrogen bond loops, providing a physical and expedite way to change the proton configuration. Here, a key ingredient of this approach is a machine learning potential trained with density functional theory data and capable of modelling molecular dissociation. We exemplify the usefulness of this idea by studying the order-disorder transition using an appropriate order parameter that distinguishes the proton environments in ice Ih and XI. We calculate the changes in free energy, enthalpy, and entropy associated with the transition. Our estimated entropy agrees with experiment within the error bars of the calculation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Adaptive pruning-based optimization of parameterized quantum circuits

Abstract Variational hybrid quantum–classical algorithms are powerful tools to maximize the use of noisy intermediate-scale quantum devices. While past studies have developed powerful and expressive ansatze, their near-term applications have been limited by the difficulty of optimizing in the vast parameter space. In this work, we propose a heuristic optimization strategy for such ansatze used in variational quantum algorithms, which we call ‘parameter-efficient circuit training (PECT)’. Instead of optimizing all of the ansatz parameters at once, PECT launches a sequence of variational algorithms, in which each iteration of the algorithm activates and optimizes a subset of the total parameter set. To update the parameter subset between iterations, we adapt the Dynamic Sparse Reparameterization scheme which was originally proposed for training deep convolutional neural networks. We demonstrate PECT for the Variational Quantum Eigensolver, in which we benchmark unitary coupled-cluster ansatze including UCCSD and k -UpCCGSD, as well as the Low-Depth Circuit Ansatz (LDCA), to estimate ground state energies of molecular systems. We additionally use a layerwise variant of PECT to optimize a hardware-efficient circuit for the Sycamore processor to estimate the ground state energy densities of the one-dimensional Fermi-Hubbard model. From our numerical data, we find that PECT can enable optimizations of certain ansatze that were previously difficult to converge and more generally can improve the performance of variational algorithms by reducing the optimization runtime and/or the depth of circuits that encode the solution candidate(s).

Physics↗
DOE OSTI2025

Neuromorphic heat transport effects in a molecular junction

Understanding energy transport at the nanoscale is an open and fundamental challenge in the molecular sciences with direct implications for the design of new electronics, computing devices, and materials. While nanoscale energy transport under steady-state conditions has been studied extensively, there is much less known about energy transport under time-dependent driving forces, particularly in the far-from-equilibrium regime. In this work, we use nonequilibrium molecular dynamics simulations and stochastic thermodynamics to investigate energy transport in a well-studied nanoscale system—a molecular junction—subjected to a time-periodic temperature gradient. The primary observation is that molecular junctions can exhibit heat transport hysteresis, a phenomenon in which the heat flux through a system depends not only on the instantaneous value of a time-dependent temperature bias but also on the temporal history of that bias. The presented findings illustrate that molecular junctions can exhibit the specific memory effect—heat transport hysteresis—that is essential for the design of thermal neuromorphic computers. This work elucidates a potential pathway toward the realization of such devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Ultrafast infrared nano-imaging of far-from-equilibrium carrier and vibrational dynamics

Ultrafast infrared nano-imaging has demonstrated access to ultrafast carrier dynamics on the nanoscale in semiconductor, correlated-electron, or polaritonic materials. However, mostly limited to short-lived transient states, the contrast obtained has remained insufficient to probe important long-lived excitations, which arise from many-body interactions induced by strong perturbation among carriers, lattice phonons, or molecular vibrations. Here, we demonstrate ultrafast infrared nano-imaging based on excitation modulation and sideband detection to characterize electron and vibration dynamics with nano- to micro-second lifetimes. As an exemplary application to quantum materials, in phase-resolved ultrafast nano-imaging of the photoinduced insulator-to-metal transition in vanadium dioxide, a distinct transient nano-domain behavior is quantified. In another application to lead halide perovskites, transient vibrational nano-FTIR spatially resolves the excited-state polaron-cation coupling underlying the photovoltaic response. These examples show how heterodyne pump-probe nano-spectroscopy with low-repetition excitation extends ultrafast infrared nano-imaging to probe elementary processes in quantum and molecular materials in space and time.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Scaling of silicon nanoparticle growth in low temperature flowing plasmas

Low temperature plasmas are an emerging method to synthesize high quality nanoparticles (NPs). An established and successful technique to produce NPs is using a capacitively coupled plasma (CCP) in cylindrical geometry. Although a robust synthesis technique, optimizing or specifying NP properties using CCPs, is challenging. In this paper, results from a computational investigation for the growth of silicon NPs in flowing inductively coupled plasmas (ICPs) using Ar/SiH 4 gas mixtures of up to a few Torr are discussed. ICPs produce more locally constrained and quiescent plasma potentials. These positive plasma potentials produce an electrostatic trap for negatively charged NPs, which can significantly extend the residence time of NPs in the plasma, which in turn provides a controllable period for particle growth. The computational platforms used in this study consist of a two-dimensional plasma hydrodynamics model, a three-dimensional nanoparticle growth and trajectory tracking model, and a molecular dynamics simulation for deriving reactive sticking coefficients of silane radicals on Si NPs. Trends for the nanoparticle growth as a function of SiH 4 inlet fraction, gas residence time, energy deposition per particle, pressure, and reactor diameter are discussed. The general path for particle synthesis is the trapping of small NPs in the positive electrostatic potential, followed by entrainment in the gas flow upon reaching a critical particle size. Optimizing or controlling NP synthesis then depends on the spatial distribution of plasma potential, the density of growth species, and the relative time that particles spend in the electrostatic trap and flowing through higher densities of growth species upon leaving the trap.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Multiscale Microtubule Dynamics in Active Nematics

In microtubule-based active nematics, motor-driven extensile motion of microtubule bundles powers chaotic large-scale dynamics. We quantify the interfilament sliding motion both in isolated bundles and in a dense active nematic. The extension speed of an isolated microtubule pair is comparable to the molecular motor stepping speed. In contrast, the net extension in dense 2D active nematics is significantly slower; the interfilament sliding speeds are widely distributed about the average and the filaments exhibit both contractile and extensile relative motion. These measurements highlight the challenge of connecting the extension rate of isolated bundles to the multimotor and multifilament interactions present in a dense 2D active nematic. Furthermore, they also provide quantitative data that is essential for building multiscale models.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Fragmentation Dynamics of Fluorene Explored Using Ultrafast XUV-Vis Pump-Probe Spectroscopy

We report on the use of extreme ultraviolet (XUV, 30.3 nm) radiation from the Free-electron LASer in Hamburg (FLASH) and visible (Vis, 405 nm) photons from an optical laser to investigate the relaxation and fragmentation dynamics of fluorene ions. The ultrashort laser pulses allow to resolve the molecular processes occurring on the femtosecond timescales. Fluorene is a prototypical small polycyclic aromatic hydrocarbon (PAH). Through their infrared emission signature, PAHs have been shown to be ubiquitous in the universe, and they are assumed to play an important role in the chemistry of the interstellar medium. Our experiments track the ionization and dissociative ionization products of fluorene through time-of-flight mass spectrometry and velocity-map imaging. Multiple processes involved in the formation of each of the fragment ions are disentangled through analysis of the ion images. The relaxation lifetimes of the excited fluorene monocation and dication obtained through the fragment formation channels are reported to be in the range of a few tens of femtoseconds to a few picoseconds.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Sequence-selective dynamic covalent assembly of information-bearing oligomers

Relatively robust dynamic covalent interactions have been employed extensively to mediate molecular self-assembly reactions; however, these assembly processes often do not converge to a thermodynamic equilibrium, instead yielding mixtures of kinetically-trapped species. Here, we report a dynamic covalent self-assembly process that mitigates kinetic trapping such that multiple unique oligomers bearing covalently coreactive pendant groups are able to undergo simultaneous, sequence-selective hybridization with their complementary strands to afford biomimetic, in-registry molecular ladders with covalent rungs. Analogous to the thermal cycling commonly employed for nucleic acid melting and annealing, this is achieved by raising and lowering the concentration of a multi-role reagent to effect quantitative dissociation and subsequently catalyze covalent bond rearrangement, affording selective assembly of the oligomeric sequences. The hybridization specificity afforded by this process further enabled information encoded in oligomers to be retrieved through selective hybridization with complementary, mass-labeled sequences.

36 MATERIALS SCIENCE↗