Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “INTERMEDIATE STATE”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Learning with Delayed Rewards—A Case Study on Inverse Defect Design in 2D Materials

Defect dynamics in materials are of central importance to a broad range of technologies from catalysis to energy storage systems to microelectronics. Material functionality depends strongly on the nature and organization of defects-their arrangements often involve intermediate or transient states that present a high barrier for transformation. The lack of knowledge of these intermediate states and the presence of this energy barrier presents a serious challenge for inverse defect design, especially for gradient-based approaches. Here, we present a reinforcement learning (RL) [Monte Carlo Tree Search (MCTS)] based on delayed rewards that allow for efficient search of the defect configurational space and allows us to identify optimal defect arrangements in low-dimensional materials. Using a representative case of two-dimensional MoS 2 , we demonstrate that the use of delayed rewards allows us to efficiently sample the defect configurational space and overcome the energy barrier for a wide range of defect concentrations (from 1.5 to 8% S vacancies)-the system evolves from an initial randomly distributed S vacancies to one with extended S line defects consistent with previous experimental studies. Detailed analysis in the feature space allows us to identify the optimal pathways for this defect transformation and arrangement. Comparison with other global optimization schemes like genetic algorithms suggests that the MCTS with delayed rewards takes fewer evaluations and arrives at a better quality of the solution. The implications of the various sampled defect configurations on the 2H to 1T phase transitions in MoS 2 are discussed. In this study, we introduce a RL strategy employing delayed rewards that can accelerate the inverse design of defects in materials for achieving targeted functionality.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Structural isomers of the S 2 state in photosystem II: do they exist at room temperature and are they important for function?

In nature, an oxo‐bridged Mn 4 CaO 5 cluster embedded in photosystem II (PSII), a membrane‐bound multi‐subunit pigment protein complex, catalyzes the water oxidation reaction that is driven by light‐induced charge separations in the reaction center of PSII. The Mn 4 CaO 5 cluster accumulates four oxidizing equivalents to enable the four‐electron four‐proton catalysis of two water molecules to one dioxygen molecule and cycles through five intermediate S‐states, S 0 – S 4 in the Kok cycle. One important question related to the catalytic mechanism of the oxygen‐evolving complex (OEC) that remains is, whether structural isomers are present in some of the intermediate S‐states and if such equilibria are essential for the mechanism of the O‐O bond formation. Here we compare results from electron paramagnetic resonance (EPR) and X‐ray absorption spectroscopy (XAS) obtained at cryogenic temperatures for the S 2 state of PSII with structural data collected of the S 1 , S 2 and S 3 states by serial crystallography at neutral pH (∼6.5) using an X‐ray free electron laser at room temperature. While the cryogenic data show the presence of at least two structural forms of the S 2 state, the room temperature crystallography data can be well‐described by just one S 2 structure. We discuss the deviating results and outline experimental strategies for clarifying this mechanistically important question.

Chatterjee, Ruchira↗
DOE OSTI2020

Kinetic Pathways Templated by Low-Temperature Intermediates during Solid-State Synthesis of Layered Oxides

Layered oxides have been the dominant cathodes in lithium-ion batteries, and among them, high-nickel (Ni) systems are attractive because of their high capacity. For practical use, synthetic control of stoichiometry and structural ordering is crucial but has been nontrivial due to the complexity inherent to synthesis reactions, which often proceed via nonequilibrium pathways. In this paper, we report here a combined in situ synchrotron X-ray diffraction and ab initio study of solid-state synthesis of layered oxides starting from acetate precursors for LiCoO 2 and LiNiO 2 and their solid solution LiNi 0.8 Co 0.2 O 2 . While all three systems ultimately evolve into the same thermodynamically stable layered phase ($R\overline{3}m$), each chemistry involves distinct metastable intermediates. We explain the phase progressions using a structural template model, demonstrating that during the synthesis of LiCoO 2 , the formed metastable spinel polymorph (Li 2 Co 2 O 4 ; $Fd\overline{3}m$) is a kinetically facile lithiation product of spinel Co 3 O 4 —the low-temperature (LT) intermediate from the decomposed Co-acetate. Similarly, in the Ni-based systems, the acetate decomposition products, rocksalts (Ni,Co)O, topotactically template the kinetic pathways of forming disordered rocksalts (Li x (Ni,Co) 2–x O 2 ; $Fm\overline{3}m$), consequently leading to off-stoichiometric Li x (Ni,Co)O 2 with undesired high Li/Ni mixing. These findings highlight new opportunities for engineering precursors to form LT intermediates that template the synthesis of target phases and structural properties.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Symmetry-Breaking Charge Transfer in Metal–Organic Frameworks

High quantum-yield charge carrier generation from the initially prepared excitons defines a key step in the light-harvesting and conversion scheme. Photoinduced charge transfer in molecular electron donor—acceptor assemblies is driven by a sizable ΔG 0 , which compromises the potential of the generated carriers. Reminiscent of the special pair at the reaction center of the natural light-harvesting complex, symmetry-breaking charge transfer (SBCT) within a pair of identical struts of metal-organic framework (MOF) will facilitate the efficient generation of long-lived charge carriers with maximized potentials without incorporating any foreign redox species. We report SBCT in pyrene-based zirconium metal–organic framework (MOF) NU-1000 that leads to efficient generation of radical ions in a polar solvent and bound CT states in a low-polar solvent. Further, the probe unveils the role of the low-lying non-Franck–Condon excitonic states as intermediates in the formation of the SBCT state from the initially prepared Franck–Condon S 1 states. Ultrafast and transient spectroscopy—probed over 200 fs-30 μs time scale-evinces a k SBCT = (110 ps) -1 in polar media (ε s = 37.5) forming solvated radical ions with recombination rate k CR = (~45 ns) -1 . A slower rate with k SBCT = (203 ps) -1 was recorded in low-polar (ε s = 7.0) solvent manifesting a bound [TBAPy •+ TBAPy •– ] state with k CR ≈ (17 μs) -1 . This discovery, along with other unique photophysical features relevant to light harvesting, should define a MOF-based platform for developing heterogeneous artificial photon energy conversion systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2010

Study of the two pion final state photoproduction on deuterium

Understanding the structure of baryons in terms of the fundamental interaction of the constituent quarks and gluons is one of the challenges in strong interaction physics. This interaction is governed by Quantum Chromodynamics (QCD). However, solutions of this theory in the non-perturbative domain of the interaction are extremely difficult to achieve. In inelastic electron scattering, very little is known about exclusive hadron production purely contributed to a lack of knowledge. The {gamma}N interaction is recognized for being a powerful method for investigating hadrons and the mysteries that still exist within the strong interaction. From reactions with the nucleon, the strong interaction can be tested through the amplitudes of the N and {Delta} resonances. More specifically, if an electromagnetic interaction is well known then the intermediate resonance states may be evaluated through pion photoproduction. To gain more detailed insight into this interaction, we look to probe the baryon structure of {Delta} and the meson structure of the pion through photon scattering off a deuteron producing two pions in the final state. The photoproduction processes on the deuteron will be used to investigate known baryon resonances in the proton-pion channel. The two pion final state will be investigated for unraveling new information in to the rho decay at threshold. We want to explore both final states interactions to search for ''missing'' states that are predicted by quark models but have not yet been found experimentally. Using the CEBAF Large Acceptance Spectrometer (CLAS), the hadronic products are detected in coincidence with the scattered photon. This makes it possible to measure the differential cross section and the decay angular distribution for the production of two and three pion final states. The measured cross sections will contribute significantly and push the knowledge of the strong interaction to the next level. We propose to use the CEBAF Large Acceptance Spectrometer (CLAS) to study the two pion channel from the EG3 data set, for {Delta}{sup ++}(1232) production. We look to investigate the exclusive reaction of {gamma}d{yields}p{pi}{sup +{pi}-}(n), extracting the relevant cross sections to comparable data sets. This reaction is produced using a high intensity photon beam incident on a deuterium target. These measurements provide unique and coherent results from tagged photons over a broad range of energy, and represent the only pion production data above 5 GeV at this present time.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2015

THE C({sup 3}P) + NH{sub 3} REACTION IN INTERSTELLAR CHEMISTRY. I. INVESTIGATION OF THE PRODUCT FORMATION CHANNELS

The product formation channels of ground state carbon atoms, C({sup 3}P), reacting with ammonia, NH{sub 3}, have been investigated using two complementary experiments and electronic structure calculations. Reaction products are detected in a gas flow tube experiment (330 K, 4 Torr) using tunable vacuum-ultraviolet (VUV) photoionization coupled with time of flight mass spectrometry. Temporal profiles of the species formed and photoionization spectra are used to identify primary products of the C + NH{sub 3} reaction. In addition, H-atom formation is monitored by VUV laser induced fluorescence (LIF) from room temperature to 50 K in a supersonic gas flow generated by the Laval nozzle technique. Electronic structure calculations are performed to derive intermediates, transition states, and complexes formed along the reaction coordinate. The combination of photoionization and LIF experiments supported by theoretical calculations indicate that in the temperature and pressure range investigated, the H + H{sub 2}CN production channel represents 100% of the product yield for this reaction. Kinetics measurements of the title reaction down to 50 K and the effect of the new rate constants on interstellar nitrogen hydride abundances using a model of dense interstellar clouds are reported in Paper II.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2010

A model for the Delta(1600) resonance and gamma N -> Delta(1600) transition

A covariant spectator constituent quark model is applied to study the gamma N -> Delta(1600) transition. Two processes are important in the transition: a photon couples to the individual quarks of the Delta(1600) core (quark core), and a photon couples to the intermediate pion-baryon states (pion cloud). While the quark core contributions are estimated assuming Delta(1600) as the first radial excitation of Delta(1232), the pion cloud contributions are estimated based on an analogy with the gamma N -> Delta(1232) transition. To estimate the pion cloud contributions in the gamma N -> Delta(1600) transition, we include the relevant intermediate states, pi-N, pi-Delta, pi-N(1440) and pi-Delta(1600). Dependence on the four-momentum transfer squared, Q2, is predicted for the magnetic dipole transition form factor, GM*(Q2), as well as the helicity amplitudes, A_1/2(Q2) and A_3/2(Q2). The results at Q2=0 are compared with the existing data.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2013

Evidence of irreversible CO2 intercalation in montmorillonite

Mitigation of the global climate change via sequestration of anthropogenic carbon dioxide (CO2) in geologic formations requires assessment of the reservoir storage capacity and cap rock seal integrity. The typical cap rock is shale or mudstone rich in clay minerals that may significantly affect the effectiveness of the CO2 trapping. Specific objectives of this study were to conduct experimental investigation into the processes associated with CO2 and H2O trapped in swelling clay, namely, Wyoming and Texas montmorillonite powder. Combined (same-sample) multi-technique data ? manometric sorption isotherm hysteresis, diffuse reflectance infrared spectroscopy ?trapped CO2? fingerprints, irreversible X-ray diffraction patterns for the clay interlayer in intermediate hydration state, and HF acid digestion resulting in formation of non-extractable F:CO2 adducts ? corroborate a hypothesis that carbon dioxide molecules can be irreversibly trapped via anomalous extreme confinement in the galleries associated with montmorillonite interlayer, which may result in formation of carbonates in the longer term. Validation on Arizona montmorillonite lumps substantiated the evidence that such processes may occur in natural clay deposits but possibly on a different scale and at a different rate.

Romanov, V↗
DOE OSTI2014

In situ electric field induced domain evolution in Ba(Zr{sub 0.2}Ti{sub 0.8})O{sub 3}-0.3(Ba{sub 0.7}Ca{sub 0.3})TiO{sub 3} ferroelectrics

In this work, the lead-free Ba(Zr{sub 0.2}Ti{sub 0.8})O{sub 3}-0.3(Ba{sub 0.7}Ca{sub 0.3})TiO{sub 3} piezoelectric ceramic was investigated in situ under an applied electric field by transmission electron microscopy. Significant changes in domain morphology of the studied material have been observed under an applied electric field. During the poling process, the domain configurations disappeared, forming a single-domain state. This multi- to single-domain state transition occurred with the formation of an intermediate nanodomain state. After removing the electric field, domain configurations reappeared. Selected area electron diffraction during electrical poling gave no indication of any structural changes as for example reflection splitting. Rather, a contribution of the extrinsic effect to the piezoelectric response of the Ba(Zr{sub 0.2}Ti{sub 0.8})O{sub 3}-0.3(Ba{sub 0.7}Ca{sub 0.3})TiO{sub 3} was found to be dominant.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2010

Superfluidity and Dimerization in a Multilayered System of Fermionic Polar Molecules

We consider a layered system of fermionic molecules with permanent dipole moments aligned perpendicular to the layers by an external field. The dipole interactions between fermions in adjacent layers are attractive and induce interlayer pairing. Because of the competition for pairing among adjacent layers, the mean-field ground state of the layered system is a dimerized superfluid, with pairing only between every other layer. We construct an effective Ising-XY lattice model that describes the interplay between dimerization and superfluid phase fluctuations. In addition to the dimerized superfluid ground state, and high-temperature normal state, at intermediate temperature, we find an unusual dimerized ''pseudogap'' state with only short-range phase coherence. We propose light-scattering experiments to detect dimerization.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Quantum Algorithm for High Energy Physics Simulations

Simulating quantum field theories is a flagship application of quantum computing. However, calculating experimentally relevant high energy scattering amplitudes entirely on a quantum computer is prohibitively difficult. It is well known that such high energy scattering processes can be factored into pieces that can be computed using well established perturbative techniques, and pieces which currently have to be simulated using classical Markov chain algorithms. These classical Markov chain simulation approaches work well to capture many of the salient features, but cannot capture all quantum effects. To exploit quantum resources in the most efficient way, we introduce a new paradigm for quantum algorithms in field theories. This approach uses quantum computers only for those parts of the problem which are not computable using existing techniques. In particular, we develop a polynomial time quantum final state shower that accurately models the effects of intermediate spin states similar to those present in high energy electroweak showers with a global evolution variable. The algorithm is explicitly demonstrated for a simplified quantum field theory on a quantum computer.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS2001

X-Ray Spectra of VY Scl Stars Are Not Blackbodies

Using ASCA data, we find, contrary to other researchers using ROSAT data, that the X, ray spectra of the VY Scl stars TT Ari and KR Aur are poorly fit by an absorbed blackbody model but are well fit by an absorbed thermal plasma model. The different conclusions about the nature of the X-ray spectrum of KR Aur may be due to differences in the accretion rate, since this star was in a high optical state during the ROSAT observation, but in an intermediate optical state during the ASCA observation. TT Ari, on the other hand, was in a high optical state during both observations, so directly contradicts the hypothesis that the X-ray spectra of VY Sol stars in their high optical states are blackbodies. Instead, based on theoretical expectations and the ASCA, Chandra, and XMM spectra of other nonmagnetic cataclysmic variables, we believe that the X-ray spectra of VY Sol stars in their low and high optical states are due to hot thermal plasma in the boundary layer between the accretion disk and the surface of the white dwarf, and appeal to the acquisition of Chandra and XMM grating spectra to test this prediction.

Mauche, C. W.↗
DOE OSTI2012

Modified Magnetic Ground State in Nimn 2 O 4 Thin Films

The authors demonstrate the stabilization of a magnetic ground state in epitaxial NiMn 2 O 4 (NMO) thin films not observed in their bulk counterpart. Bulk NMO exhibits a magnetic transition from a paramagnetic phase to a collinear ferrimagnetic moment configuration below 110 K and to a canted moment configuration below 70 K. By contrast, as-grown NMO films exhibit a single magnetic transition at 60 K and annealed films exhibit the magnetic behavior found in bulk. Cation inversion and epitaxial strain are ruled out as possible causes for the new magnetic ground state in the as-grown films. However, a decrease in the octahedral Mn 4+ :Mn 3+ } concentration is observed and likely disrupts the double exchange that produces the magnetic state at intermediate temperatures. X-ray magnetic circular dichroism and bulk magnetometry indicate a canted ferrimagnetic state in all samples at low T. Together these results suggest that the collinear ferrimagnetic state observed in bulk NMO at intermediate temperatures is suppressed in the as grown NMO thin films due to a decrease in octahedral Mn 4+ , while the canted moment ferrimagnetic ordering is preserved below 60 K.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2010

Modified magnetic ground state in NiMn2O4 thin films

We demonstrate the stabilization of a magnetic ground state in epitaxial NiMn2O4 (NMO) thin films not observed in their bulk counterpart. Bulk NMO exhibits a magnetic transition from a paramagnetic phase to a collinear ferrimagnetic moment configuration below 110 K and to a canted moment configuration below 70 K. By contrast, as-grown NMO films exhibit a single magnetic transition at 60 K and annealed films exhibit the magnetic behavior found in bulk. Cation inversion and epitaxial strain are ruled out as possible causes for the new magnetic ground state in the as-grown films. However, a decrease in the octahedral Mn{sup 4+}:Mn{sup 3+} concentration is observed and likely disrupts the double exchange that produces the magnetic state at intermediate temperatures. X-ray magnetic circular dichroism and bulk magnetometry indicate a canted ferrimagnetic state in all samples at low temperature. Together these results suggest that the collinear ferrimagnetic state observed in bulk NMO at intermediate temperatures is suppressed in the as grown NMO thin films due to a decrease in octahedral Mn{sup 4+} while the canted moment ferrimagnetic ordering is preserved below 60 K.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Apparent Activation Energies in Complex Reaction Mechanisms: A Simple Relationship via Degrees of Rate Control

The apparent activation energy of chemical reactions previously played a central role in the field of chemical kinetics and has served as an important tool for analyzing and understanding reaction rates, mechanistic details of complex reaction mechanisms, elementary-step energetics, catalytic activity and reaction selectivity. In this work, we derive a general expression which shows that the apparent activation energy equals a weighted average of the standard-state enthalpies (relative to reactants) of all the species (intermediates, transition states and products) in the reaction mechanism, each weighted by its generalized degree of rate control (DRC). Since the DRC is zero for most of these species, even in very complex mechanisms, the weighted average includes only a few terms. This simplicity provides deep insight into the connection between the reaction energy diagram and the apparent activation energy. We prove both this and the quantitative validity of this equation by analysis of numerous reaction mechanisms. We also show the failures or weaknesses of previous equations for the apparent activation energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Cross sections for 14-eV e-H{sub 2} resonant collisions: Isotope effect in dissociative electron attachment

The process of dissociative attachment of electrons to molecular hydrogen and its isotopes in the energy range at approximately 14 eV is investigated. The dissociative electron attachment cross sections for all six hydrogen isotopes are calculated over an extended range of electron energies using the local complex potential model with the excited Rydberg {sup 2}{Sigma}{sub g}{sup +} electronic state of H{sub 2}{sup -} acting as the intermediate resonant state. A significant isotope effect in theoretical electron attachment cross sections is observed, in agreement with previous predictions and experimental observations. A two-parameter analytic expression for the cross section is derived from the theory that fits accurately the numerically calculated cross sections for all isotopes. Similarly, an analytic mass-scaling relation is derived from the theory that accurately reproduces the numerically calculated rate coefficients for all isotopes in the 0.1-1000 eV temperature range by using the rate coefficient for the H{sub 2} isotope only. The latter is represented by an analytic fit expression with two parameters only.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Data-driven prediction of α IIb β 3 integrin activation paths using manifold learning and deep generative modeling

The integrin heterodimer is a transmembrane protein critical for driving cellular process and is a therapeutic target in the treatment of multiple diseases linked to its malfunction. Activation of integrin involves conformational transitions between bent and extended states. Some of the conformations that are intermediate between bent and extended states of the heterodimer have been experimentally characterized, but the full activation pathways remain unresolved both experimentally due to their transient nature and computationally due to the challenges in simulating rare barrier crossing events in these large molecular systems. An understanding of the activation pathways can provide new fundamental understanding of the biophysical processes associated with the dynamic interconversions between bent and extended states and unveil new putative therapeutic targets. In this work, we apply nonlinear manifold learning to coarse-grained molecular dynamics simulations of bent, extended, and two intermediate states of αI I b β3 integrin to learn a low-dimensional embedding of the configurational phase space. We then train deep generative models to learn an inverse mapping between the low-dimensional embedding and high-dimensional molecular space and use these models to interpolate the molecular configurations constituting the activation pathways between the experimentally characterized states. Furthermore, this work furnishes plausible predictions of integrin activation pathways and reports a generic and transferable multi-scale technique to predict transition pathways for biomolecular systems.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2023

Disordered interfaces of alkaline aluminate salt hydrates provide glimpses of Al 3+ coordination changes

Hypothesis: The precipitation and dissolution of aluminum-bearing mineral phases in aqueous systems often proceed via changes in both aluminum coordination number and connectivity, complicating molecular-scale interpretation of the transformation mechanism. Here, the thermally induced transformation of crystalline sodium aluminum salt hydrate, a phase comprised of monomeric octahedrally coordinated aluminate which is of relevance to industrial aluminum processing, has been studied. Because intermediate aluminum coordination states during melting have not previously been detected, it is hypothesized that the transition to lower coordinated aluminum ions occurs within a highly disordered quasi-two-dimensional phase at the solid-solution interface. Experiments and simulations: In this work, in situ X-ray diffraction (XRD), Raman and 27 Al nuclear magnetic resonance (NMR) spectroscopy were used to monitor the melting transition of nonasodium aluminate hydrate (NSA, Na 9 [Al(OH) 6 ] 2 ·3(OH)·6H 2 O). A mechanistic interpretation was developed based on complementary classical molecular dynamics (CMD) simulations including enhanced sampling. A reactive forcefield was developed to bridge speciation in the solution and in the solid phase. Findings: In contrast to classical dissolution, aluminum coordination change proceeds through a dynamically stabilized ensemble of intermediate states in a disordered layer at the solid-solution interface. In both melting and dissolution of NSA, octahedral, monomeric aluminum transition through an intermediate of pentahedral coordination. The intermediate dehydroxylates to form tetrahedral aluminate (Al(OH)$_4^–$) in the liquid phase. This coordination change is concomitant with a breaking of the ionic aluminate-sodium ion linkages. The solution phase Al(OH)$_4^–$ ions subsequently polymerize into polynuclear aluminate ions. However, there are some differences between bulk melting and interfacial dissolution, with the onset of the surface-controlled process occurring at a lower temperature (~30 °C) and the coordination change taking place more gradually as a function of temperature. This work to determine the local structure and dynamics of aluminum in the disordered layer provides a new basis to understand mechanisms controlling aluminum phase transformations in highly alkaline solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗