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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Persistence of Spin Coherence in a Crystalline Environment

Here, we analyze quantum interference in the triplet-exciton pair generated by singlet exciton fission in a molecular crystal and introduce transport-induced dephasing (TID) as a key effect that can suppress the expected fluorescence quantum beats when the triplet-exciton wave function can localize on inequivalent sites. TID depends on the triplet-exciton hopping rate between inequivalent sites and on the energy shifts among the stationary states of the entangled triplet pair in different spatial configurations. The theoretical model is confirmed by experiments in rubrene single crystals, where triplet pairs remain entangled for more than 50 ns but quantum beats are suppressed by TID within a few nanoseconds when the magnetic field is misaligned by just a few degrees from specific symmetric directions. Our experiments deliver the zero-field parameters for the rubrene molecule in its orthorhombic lattice and information on triplet-exciton transport, in particular, the triplet-exciton hopping rate between inequivalent sites, which we evaluate to be of the order of 150 ps in rubrene.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Subsurface Spectroscopy of Thermal Degradation Inside an Inert Plastic Bonded Explosive (PBX) Simulant Using Feedback-Assisted Wavefront Shaping

We characterize the subsurface thermal degradation of an inert analog of high-explosive molecular crystals (Eu:Y(acac) 3 (DPEPO)) (EYAD) embedded inside of a plastic bonded explosive simulant using feedback-assisted wavefront shaping-based fluorescence and Raman spectroscopies. This technique utilizes wavefront shaping to focus pump light inside a heterogeneous material onto a target particle, which significantly improves its spectroscopic signature. We find that embedding the EYAD crystals in the heterogeneous polymer results in improved thermal stability, relative to bare crystal measurements, with the crystal remaining fluorescent to >612 K inside of the heterogeneous material, while the bare crystal’s fluorescence is fully quenched by 500 K. We hypothesize that this improvement is due to the polymer restricting the effects of EYAD melting, which occurs at 400 K and is the primary mechanism for spectroscopic changes in the temperature range explored.

Anderson, Benjamin R.↗
DOE OSTI2022

Compressive strength of the plastic-bonded explosive surrogate idoxuridine under quasistatic and dynamic compression

Inert simulant materials, or “mocks”, are often used as surrogates for plastic-bonded explosives (PBX) in non-detonative tests in order to mitigate hazards. Mocks should reproduce as many non-detonative properties of the explosive as possible, including structural behavior in a variety of thermal and mechanical environments. Recently, the molecular crystal idoxuridine (IDOX) has been identified as an ideal mock for the main component in the explosive polymer-matrix composite PBX 9501, and has performed favorably under quasistatic loading conditions. Here, in order to assess robustness over a range of mechanical environments, plastic-bonded IDOX was compression tested from 0.001/s to 2000/s strain rates and compared to PBX 9501 historical data. Plastic-bonded IDOX showed good agreement to PBX 9501 across these strain rates, justifying continued development and production as a mock.

Burch, Alexandra C.↗
DOE OSTI2024

Design, Control and Application of Next Generation Qubits

Design, Control and Application of Next Generation Qubits Arun Bansil, Northeastern University (Principal Investigator) Claudio Chamon, Boston University (Co-Investigator) Adrian Feiguin, Northeastern University (Co-Investigator) Liang Fu, MIT (Co-Investigator) Eduardo Mucciolo, Univ. of Central Florida (Co-Investigator) Qimin Yan, Temple University (Co-Investigator) The quest for developing technologies for manipulating and storing information quantum mechanically is currently led by approaches that include Josephson-junctions, ion-traps, and qubits generated by defect spins in solids. Topological qubits, however, are inherently more robust to decoherence by environmental effects, and should be able to sprint ahead once practical barriers have been overcome. At the present stage of the development of the field, it is important to explore a variety of architectures and materials beyond the conventional paradigms in order to seed breakthroughs toward building a scalable quantum computer. Our comprehensive theoretical research program involved four interconnected thrusts as follows. • A materials discovery effort in two-dimensional compounds in search of materials to support Majorana zero modes and defect structures suitable as qubits. • Exploration of architectures for topological quantum computation by investigating both superconducting Majorana qubits, and robust platforms for braiding with new “meta-materials” built of arrays of Majorana qubits. • Investigation of properties of hybrid metal-organic qubits based on transition-metal centers in graphene, and molecular crystals of polyaromatic complexes with embedded transition-metal atoms. • Development of tensor-network and semiclassical approaches to study decoherence in the presence of random and dispersive spin baths, and NV centers in diamond. The full spectrum of theoretical and numerical approaches was used to address the goals of this project including first-principles, density-matrix-renormalization group, tensor networks, and data-driven high-throughput approaches using materials database and machine-learning.

36 MATERIALS SCIENCE↗
NASA NTRS1972

Infrared spectra of molecules and materials of astrophysical interest

Vibrational spectra were studied from 400 to 33/cm for molecules which may be present in the atmosphere of Jovian planets. The microwave spectrum of cis glyoxal was studied. Sources of color variation in the Jovian atmosphere were analyzed in relation to molecular crystals. The low frequency modes of acetaldehyde and acetaldehyde-d sub 4 are discussed.

Durig, J. R.↗
NASA NTRS1981

Two-component Fermi-liquid theory - Equilibrium properties of liquid metallic hydrogen

It is reported that the transition of condensed hydrogen from an insulating molecular crystal phase to a metallic liquid phase, at zero temperature and high pressure, appears possible. Liquid metallic hydrogen (LMH), comprising interpenetrating proton and electron fluids, would constitute a two-component Fermi liquid with both a very high component-mass ratio and long-range, species-dependent bare interactions. The low-temperature equilibrium properties of LMH are examined by means of a generalization to the case of two components of the phenomenological Landau Fermi-liquid theory, and the low-temperature specific heat, compressibility, thermal expansion coefficient and spin susceptibility are given. It is found that the specific heat and the thermal expansion coefficient are vastly greater in the liquid than in the corresponding solid, due to the presence of proton quasiparticle excitations in the liquid.

Oliva, J.↗
NASA NTRS1983

Experiments with phase transitions at very high pressure

Diamond cells were constructed for use to 1 Mbar. A refrigerator for cooling diamond cells was adapted for studies between 15 and 300 K. A cryostat for superconductivity studies between 1.5 to 300 K was constructed. Optical equipment was constructed for fluorescence, transmission, and reflectance studies. X-ray equipment was adapted for use with diamond cells. Experimental techniques were developed for X-ray diffraction studies using synchrotron radiation. AC susceptibility techniques were developed for detecting superconducting transitions. The following materials were studied: compressed solidified gases (Xe, Ar), semiconductors (Ge, Si, GaAs), superconductors (Nb3Ge, Nb3Si, Nb3As, CuCl), molecular crystals (I).

Spain, I. L.↗
NASA NTRS1983

Pressure dependence of intramolecular mode frequencies in solid N2, O2, and CO2

A microscopic description of the pressure dependence of intramolecular vibrational modes in simple molecular crystals has been formulated using a classical perturbation theory. Quantitative agreement with experiment is demonstrated and it is shown that frequency changes at phase transitions are large enough to be observed optically.

Etters, R. D.↗
NASA NTRS1985

Defining a national microgravity facility for America's Space Station

Plans for a Microgravity and Materials Processing Facility (with a Manufacturing and Technology Laboratory Module as its main element) on the U.S. Space Station are reviewed and illustrated with drawings, graphs, tables, and diagrams. Consideration is given to the ideal and practically achievable acceleration environment, on-orbit sample preparation and analysis, crew operations, technology-development requirements, and classes of materials with commercial potential (with an emphasis on organic molecular crystals).

Mookherji, Tripty↗
NASA NTRS2000

Microgravity Platforms

The world's space agencies have been conducting microgravity research since the beginning of space flight. Initially driven by the need to understand the impact of less than- earth gravity physics on manned space flight, microgravity research has evolved into a broad class of scientific experimentation that utilizes extreme low acceleration environments. The U.S. NASA microgravity research program supports both basic and applied research in five key areas: biotechnology - focusing on macro-molecular crystal growth as well as the use of the unique space environment to assemble and grow mammalian tissue; combustion science - focusing on the process of ignition, flame propagation, and extinction of gaseous, liquid, and solid fuels; fluid physics - including aspects of fluid dynamics and transport phenomena; fundamental physics - including the study of critical phenomena, low-temperature, atomic, and gravitational physics; and materials science - including electronic and photonic materials, glasses and ceramics, polymers, and metals and alloys. Similar activities prevail within the Chinese, European, Japanese, and Russian agencies with participation from additional international organizations as well. While scientific research remains the principal objective behind these program, all hope to drive toward commercialization to sustain a long range infrastructure which .benefits the national technology and economy. In the 1997 International Space Station Commercialization Study, conducted by the Potomac Institute for Policy Studies, some viable microgravity commercial ventures were identified, however, none appeared sufficiently robust to privately fund space access at that time. Thus, government funded micro gravity research continues on an evolutionary path with revolutionary potential.

Del Basso, Steve↗
NASA NTRS2018

Microscopes on ISS - Present and Future Possibilities

The attached slides are for an invited talk (invitation from Ken Savins at CASIS) to be given July 19 at the "2018 Microgravity Molecular Crystal Growth Workshop". Ken Savins indicated that the protein crystal growth community would benefit from knowing more about what is available on ISS for microscopy. It is especially important that the folks growing protein crystals start to use the microscopes on ISS as diagnostic tools so that when their samples are returned to Earth and the results are unexpected, they are able to determine whether or not the return flight had an impact. In additional to preparing this presentation describing present and possible future LMM capabilities (if it is refurbished), we worked with Rachel A Ormsby (techshot) and Devin Ridgley (HNu Photonics) to add slides and a movie they provided of their capacities. Contact information for the NASA GRC Liquid Crystal Facility (LCF) will be included, and a couple of slides for LCF may be added when the contractor (James Kolibas at ZIN Technology) returns from vacation.

protein crystals↗
DOE OSTI2024

Designed 2D protein crystals as dynamic molecular gatekeepers for a solid-state device

The sensitivity and responsiveness of living cells to environmental changes are enabled by dynamic protein structures, inspiring efforts to construct artificial supramolecular protein assemblies. However, despite their sophisticated structures, designed protein assemblies have yet to be incorporated into macroscale devices for real-life applications. We report a 2D crystalline protein assembly of C98/E57/E66 L-rhamnulose-1-phosphate aldolase ( CEE RhuA) that selectively blocks or passes molecular species when exposed to a chemical trigger. CEE RhuA crystals are engineered via cobalt(II) coordination bonds to undergo a coherent conformational change from a closed state (pore dimensions <1 nm) to an ajar state (pore dimensions ~4 nm) when exposed to an HCN(g) trigger. When layered onto a mesoporous silicon (pSi) photonic crystal optical sensor configured to detect HCN (g) , the 2D CEE RhuA crystal layer effectively blocks interferents that would otherwise result in a false positive signal. The 2D CEE RhuA crystal layer opens in selective response to low-ppm levels of HCN (g) , allowing analyte penetration into the pSi sensor layer for detection. These findings illustrate that designed protein assemblies can function as dynamic components of solid-state devices in non-aqueous environments.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Evaluating the active site-substrate interplay between x-ray crystal structure and molecular dynamics in chorismate mutase

Designing realistic quantum mechanical (QM) models of enzymes is dependent on reliably discerning and modeling residues, solvents, and cofactors important in crafting the active site microenvironment. Interatomic van der Waals contacts have previously demonstrated usefulness toward designing QM-models, but their measured values (and subsequent residue importance rankings) are expected to be influenceable by subtle changes in protein structure. Using chorismate mutase as a case study, this work examines the differences in ligand-residue interatomic contacts between an x-ray crystal structure and structures from a molecular dynamics simulation. Select structures are further analyzed using symmetry adapted perturbation theory to compute ab initio ligand-residue interaction energies. The findings of this study show that ligand-residue interatomic contacts measured for an x-ray crystal structure are not predictive of active site contacts from a sampling of molecular dynamics frames. In addition, the variability in interatomic contacts among structures is not correlated with variability in interaction energies. However, the results spotlight using interaction energies to characterize and rank residue importance in future computational enzymology workflows.

Chemistry↗
DOE OSTI2021

Buffered Coordination Modulation as a Means of Controlling Crystal Morphology and Molecular Diffusion in an Anisotropic Metal-Organic Framework

We know significant advances have been made in the synthesis of chemically selective environments within metal-organic frameworks, yet materials development and industrial implementation have been hindered by the inability to predictively control crystallite size and shape. One common strategy to control crystal growth is the inclusion of coordination modulators, which are molecular species designed to compete with the linker for metal coordination during synthesis. However, these modulators can simultaneously alter the pH of the reaction solution, an effect that can also significantly influence crystal morphology. Herein, noncoordinating buffers are used to independently control reaction pH during metal-organic framework synthesis, enabling direct interrogation of the role of the coordinating species on crystal growth. We demonstrate the efficacy of this strategy in the synthesis of low-dispersity single-crystals of the framework Co 2 (dobdc) (dobdc 4- = 2,5-dioxido-1,4-benzenedicarboxylate) in a pH 7-buffered solution using cobalt(II) acetate as the metal source. Density functional theory calculations reveal that acetate competitively binds to Co during crystallization, and by using a series of cobalt(II) salts with carboxylate anions of varying coordination strength, it is possible to control crystal growth along the c -direction. Finally, we use zero length column chromatography to show that crystal morphology has a direct impact on guest diffusional path length for the industrially important hydrocarbon m -xylene. Together, these results provide molecular-level insight into the use of modulators in governing crystallite morphology and a powerful strategy for the control of molecular diffusion rates within metal-organic frameworks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2023

Thermomechanical Property Prediction of Amorphous and Crystal PEKK via Molecular Dynamics

Traditionally, advanced aerospace composites have been manufactured using thermoset resins. However, recently, thermoplastics have been investigated for use in the manufacturing of composite materials due to their unique manufacturing characteristics. Thermoplastic resins can be reshaped and formed, along with the added benefit of being recyclable, which thermoset resin cannot. Thermoplastic materials undergo a crystallization process during manufacturing which affects the percent crystallinity of the material. The crystallization needs to be understood better to maximize the potential of thermoplastic resins. PEKK is a thermoplastic material with good chemical, thermal, and mechanical loading resistance. PEKK is also a material NASA is interested in for developing new bonded joint technology. The crystalline microstructure of PEKK is at the micrometer length scale, and it is of interest to model the effects of the crystallinity structure on PEKK’s bulk properties. Molecular dynamics (MD) is a simulation tool that allows for property-structure relationships between atomistic structure and nanometer-length portions of a material. This makes MD a useful tool for developing the structure-property relationship of PEKK. However, the micrometer length scale of PEKK’s crystal structure is too large for MD. Thus, a hybrid approach to modeling PEKK’s microstructure is proposed in this work where MD models are built of both the amorphous and crystalline phases of PEKK. The engineering material properties can be obtained using MD at the nanometer length scale. A micromechanics approach can then generate the micrometer length scale of the crystallinity and the effective properties can be homogenized. The objective of this paper is to show the MD model workflow and the MD-predicted properties of PEKK. The properties can then be homogenized with different crystalline percentages to build design graphs that can be used to tailor PEKK for specific composite applications.

poly ether ketone ketone↗