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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 919 records · Page 51
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Control of chemical reactivity by transition-state and beyond

It has been long established that the transition state for an activated reaction controls the overall reactivity, serving as the bottleneck for reaction flux. However, the role of the transition state in regulating quantum state resolved reactivity has only been addressed more recently, thanks to advances in both experimental and theoretical techniques. Here in this perspective, we discuss some recent advances in understanding mode-specific reaction dynamics in bimolecular reactions, mainly focusing on the X + H 2 O/CH 4 (X = H, F, Cl, and O( 3 P)) systems, extensively studied in our groups. These advances shed valuable light on the importance of the transition state in mode-specific and steric dynamics of these prototypical reactions. It is shown that many mode-specific phenomena can be understood in terms of a transition-state based model, which assumes in the sudden limit that the ability of a reactant mode for promoting the reaction stems from its coupling with the reaction coordinate at the transition state. Yet, in some cases the long-range anisotropic interactions in the entrance (or exit) valley, which govern how the trajectories reach (or leave) the transition state, also come into play, thus modifying the reactive outcomes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Metal–insulator transition tuned by magnetic field in Bi 1.7 V 8 O 16 hollandite

A metal–insulator transition tuned by application of an external magnetic field occurs in the quasi-one dimensional system Bi1.7V8O16, which contains a mix of S = 1 and S = 1/2 vanadium cations. Unlike all other known vanadates, the magnetic susceptibility of Bi1.7V8O16 diverges in its insulating state, although no long-range magnetic ordering is observed from neutron diffraction measurements, possibly due to the frustrated geometry of the triangular ladders. Magnetotransport measurements reveal that the transition temperature is suppressed upon application of an external magnetic field, from 62.5 K at zero field to 40 K at 8 T. This behavior is both hysteretic and anisotropic, suggesting t2g orbital ordering of the V3+ and V4+ cations drives a first-order structural transition. Single crystal X-ray diffraction reveals a charge density wave of Bi3+ cations with a propagation vector of 0.846c*, which runs parallel to the triangular chain direction. Neutron powder diffraction measurements show a first-order structural transition, characterized by the coexistence of two tetragonal phases near the metal–insulator transition. Finally, we discuss the likelihood that ferromagnetic V–V dimers coexist with a majority spin-singlet state below the transition in Bi1.7V8O16.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Anomalous phase transition behavior in hydrothermal grown layered tellurene

Recent studies have demonstrated that tellurene is a van der Waals (vdW) two-dimensional material with potential optoelectronic and thermoelectric applications as a result of its pseudo-one-dimensional structure and properties. Here, we report on the pressure induced anomalous phase transition of tellurium nanoribbons. The observation of clean phase transitions was made possible with high quality single crystalline Te nanoribbons that are synthesized by hydrothermal reaction growth. The results show that phase transition has a large pressure hysteresis and multiple competing phases: during compression, the phase transition is sudden and takes place from trigonal to orthorhombic phase at 6.5 GPa. Orthorhombic phase remains stable up to higher pressures (15 GPa). In contrast, phase transition is not sudden during decompression, but orthorhombic and trigonal phases co-exist between 6.9 to 3.4 GPa. Grüneisen parameter calculations further confirm the presence of co-existing phases and suggest hysteretic phase change behavior. Finally, orthorhombic to trigonal phase transition occurs at 3.4 GPa which means overall pressure hysteresis is around 3.1 GPa.

42 ENGINEERING↗
DOE OSTI2014

On the existence of vapor-liquid phase transition in dusty plasmas

The phenomenon of phase transition in a dusty-plasma system (DPS) has attracted some attention in the past. Earlier Farouki and Hamaguchi [J. Chem. Phys. 101, 9876 (1994)] have demonstrated the existence of a liquid to solid transition in DPS where the dust particles interact through a Yukawa potential. However, the question of the existence of a vapor-liquid (VL) transition in such a system remains unanswered and relatively unexplored so far. We have investigated this problem by performing extensive molecular dynamics simulations which show that the VL transition does not have a critical curve in the pressure versus volume diagram for a large range of the Yukawa screening parameter κ and the Coulomb coupling parameter Γ. Thus, the VL phase transition is found to be super-critical, meaning that this transition is continuous in the dusty plasma model given by Farouki and Hamaguchi. We provide an approximate analytic explanation of this finding by means of a simple model calculation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2015

Dynamic heterogeneity in the folding/unfolding transitions of FiP35

Molecular dynamics simulations have become an important tool in studying protein dynamics over the last few decades. Atomistic simulations on the order of micro- to milliseconds are becoming feasible and are used to study the state-of-the-art experiments in atomistic detail. Yet, analyzing the high-dimensional-long-temporal trajectory data is still a challenging task and sometimes leads to contradictory results depending on the analyses. To reveal the dynamic aspect of the trajectory, here we propose a simple approach which uses a time correlation function matrix and apply to the folding/unfolding trajectory of FiP35 WW domain [Shaw et al., Science 330, 341 (2010)]. The approach successfully characterizes the slowest mode corresponding to the folding/unfolding transitions and determines the free energy barrier indicating that FiP35 is not an incipient downhill folder. The transition dynamics analysis further reveals that the folding/unfolding transition is highly heterogeneous, e.g., the transition path time varies by ∼100 fold. We identify two misfolded states and show that the dynamic heterogeneity in the folding/unfolding transitions originates from the trajectory being trapped in the misfolded and half-folded intermediate states rather than the diffusion driven by a thermal noise. The current results help reconcile the conflicting interpretations of the folding mechanism and highlight the complexity in the folding dynamics. This further motivates the need to understand the transition dynamics beyond a simple free energy picture using simulations and single-molecule experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Tensile-strain effect of inducing the indirect-to-direct band-gap transition and reducing the band-gap energy of Ge

By means of a hybrid density-functional method, we investigate the tensile-strain effect of inducing the indirect-to-direct band-gap transition and reducing the band-gap energy of Ge. We consider [001], [111], and [110] uniaxial tensility and (001), (111), and (110) biaxial tensility. Under the condition of no normal stress, we determine both normal compression and internal strain, namely, relative displacement of two atoms in the primitive unit cell, by minimizing the total energy. We identify those strain types which can induce the band-gap transition, and evaluate the critical strain coefficient where the gap transition occurs. Either normal compression or internal strain operates unfavorably to induce the gap transition, which raises the critical strain coefficient or even blocks the transition. We also examine how each type of tensile strain decreases the band-gap energy, depending on its orientation. Our analysis clearly shows that synergistic operation of strain orientation and band anisotropy has a great influence on the gap transition and the gap energy.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Coil–globule transition of a polymer involved in excluded-volume interactions with macromolecules

Polymers adopt extended coil and compact globule states according to the balance between entropy and interaction energies. The transition of a polymer between an extended coil state and compact globule state can be induced by changing thermodynamic force such as temperature to alter the energy/entropy balance. Previously, this transition was theoretically studied by taking into account the excluded-volume interaction between monomers of a polymer chain using the partition function. For binary mixtures of a long polymer and short polymers, the coil-globule transition can be induced by changing the concentration of the shorter polymers. Here, we investigate the transition caused by short polymers by generalizing the partition function of the long polymer to include the excluded-volume effect of short polymers. The coil-globule transition is studied as a function of the concentration of mixed polymers by systematically varying Flory’s χ-parameters. We show that the transition is caused by the interplay between the excluded-volume interaction and the dispersion state of short polymers in the solvent. We also reveal that the same results can be obtained by combining the mixing entropy and elastic energy if the volume of a long polymer is properly defined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Photoreflectance study of the near-band-edge transitions of chemical vapor deposition-grown mono- and few-layer MoS{sub 2} films

Room-temperature photoreflectance (PR) and reflectance (R) spectroscopy are utilized to investigate the near-band-edge transitions of molybdenum disulfide (MoS{sub 2}) thin films grown on sapphire substrates by a hot-wall chemical vapor deposition system. The layer thickness and optical properties of the MoS{sub 2} thin films are confirmed by Raman spectroscopy, atomic force microscope, and photoluminescence (PL) analysis. The B exciton shows relatively weak PL intensity in comparing with the A exciton even for monolayer MoS{sub 2} films. In the R spectrum of few‐layer MoS{sub 2}, it is not possible to clearly observe exciton related features. The PR spectra have two sharp, derivative-like features on a featureless background. Throughout the PR lineshape fitting, the transition energies are designated as the A and B excitons at the K-point of the Brillouin zone, but at room temperature there seems to be no distinguishable feature corresponding to an H‐point transition for the mono- and few-layer MoS{sub 2} films unlike in bulk. These transition energies are slightly larger than those obtained by PL, which is attributed to the Stokes shifts related to doping level. The obtained values of valence-band spin-orbit splitting are in good agreement with those from other experimental methods. By comparing the PR lineshapes, the dominant modulation mechanism is attributed to variations of the exciton transition energies due to change in the built-in electric field. On the strength of this study, PR spectroscopy is demonstrated as a powerful technique for characterizing the near-band-edge transitions of MoS{sub 2} from monolayer to bulk.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Pressure dependence of band-gap and phase transitions in bulk CuX (X = Cl, Br, I)

Usually a phase transition, in theoretical studies, is explored or verified by studying the total energy as a function of the volume considering various plausible phases. The intersection point, if any, of the free energy vs. volume curves for the different phases is then the indicator of the phase transition(s). The question is, can the theoretical study of a single phase alone indicate a phase transition? i.e. can we look beyond the phase under consideration through such a study? Using density-functional theory, we report a novel approach to suggest phase transition(s) through theoretical study of a single phase. Copper halides have been engaged for this study. These are direct band-gap semiconductors, with zinc blende structure at ambient conditions, and are reported to exhibit many phase transitions. We show that the study of volume dependence of energy band-gap in a single phase facilitates looking beyond the phase under consideration. This, when translated to pressures, reflects the phase transition pressures for CuX (X = Cl, Br, I) with an encouraging accuracy. This work thus offers a simple, yet reliable, approach based on electronic structure calculations to investigate new semiconducting materials for phase changes under pressure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Spin transitions in La{sub 0.7} Ba{sub 0.3}CoO{sub 3} thin films revealed by combining Raman spectroscopy and X-ray diffraction

In cobaltite, the spin states transitions of Co{sup 3+/4+} ions govern the magnetic and electronic conduction properties. These transitions are strain-sensitive and can be varied using external parameters, including temperature, hydrostatic pressure, or chemical stresses through ionic substitutions. In this work, using temperature dependent Raman spectroscopy and X-ray diffraction, the epitaxial strain effects on both structural and vibrational properties of La{sub 0.7} Ba{sub 0.3} CoO{sub 3} (LBCO) cobaltite thin films are investigated. All Raman active phonon modes as well as the structure are found to be strongly affected. Both Raman modes and lattice parameter evolutions show temperature changes correlated with magnetic and electronic transitions properties. Combining Raman spectroscopy and X-ray diffraction appears as a powerful approach to probe the spin transition in thin film cobaltite. Our results provide insight into strong spin-charge-phonon coupling in LBCO thin film. This coupling manifests as vibrational transition with temperature in the Raman spectra near the ferromagnetic spin ordered transition at 220 K.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Characterization of a new Hencken burner with a transition from a reducing-to-oxidizing environment for fundamental coal studies

In pulverized coal burners, coal particles usually transition from a locally reducing environment to an oxidizing environment. The locally reducing environment in the near-burner region is due to a dense region of coal particles undergoing devolatilization. Following this region, the particles move into an oxidizing environment. This “reducing-to-oxidizing” transition can influence combustion processes such as ignition, particulate formation, and char burnout. To understand these processes at a fundamental level, a system is required that mimics such a transition. Hence, we have developed and characterized a two-stage Hencken burner to evaluate the effect of the reducing-to-oxidizing transition and particle-to-particle interaction (which characterizes dense region of coal particles) on ignition and ultrafine aerosol formation. The two-stage Hencken burner allows coal particles to experience a reducing environment followed by a transition to an oxidizing environment. Here, this work presents the results of the design and characterization of the new two-stage Hencken burner and its new coal feeder. In a unique approach to the operation of the flat-flame of the Hencken burner, the flame configurations are operated as either a normal flame or inverse flame. Gas temperatures and oxygen concentrations for the Hencken burner are measured in reducing-to-oxidizing and oxidizing environments. The results show that stable flames with well-controlled conditions, relatively uniform temperatures, and species concentrations can be achieved in both flame configurations. This new Hencken burner provides an effective system for evaluating the effect of the reducing-to-oxidizing transition and particle-to-particle interaction on early-stage processes of coal combustion such as ignition and ultrafine particle formation.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

An exploration of machine learning models for the determination of reaction coordinates associated with conformational transitions

Determining collective variables (CVs) for conformational transitions is crucial to understanding their dynamics and targeting them in enhanced sampling simulations. Often, CVs are proposed based on intuition or prior knowledge of a system. However, the problem of systematically determining a proper reaction coordinate (RC) for a specific process in terms of a set of putative CVs can be achieved using committor analysis (CA). Identifying essential degrees of freedom that govern such transitions using CA remains elusive because of the high dimensionality of the conformational space. Various schemes exist to leverage the power of machine learning (ML) to extract an RC from CA. Here, we extend these studies and compare the ability of 17 different ML schemes to identify accurate RCs associated with conformational transitions. We tested these methods on an alanine dipeptide in vacuum and on a sarcosine dipeptoid in an implicit solvent. Our comparison revealed that the light gradient boosting machine method outperforms other methods. In order to extract key features from the models, we employed Shapley Additive exPlanations analysis and compared its interpretation with the “feature importance” approach. For the alanine dipeptide, our methodology identifies ϕ and θ dihedrals as essential degrees of freedom in the C7ax to C7eq transition. For the sarcosine dipeptoid system, the dihedrals ψ and ω are the most important for the cisαD to transαD transition. We further argue that analysis of the full dynamical pathway, and not just endpoint states, is essential for identifying key degrees of freedom governing transitions.

Chemistry↗
DOE OSTI2022

Field-tuned ferroquadrupolar quantum phase transition in the insulator TmVO 4

We report results of low-temperature heat-capacity, magnetocaloric-effect, and neutron-diffraction measurements of TmVO 4 , an insulator that undergoes a continuous ferroquadrupolar phase transition associated with local partially filled 4 f orbitals of the thulium (Tm 3 + ) ions. The ferroquadrupolar transition, a realization of Ising nematicity, can be tuned to a quantum critical point by using a magnetic field oriented along the c axis of the tetragonal crystal lattice, which acts as an effective transverse field for the Ising-nematic order. In small magnetic fields, the thermal phase transition can be well described by using a semiclassical mean-field treatment of the transverse-field Ising model. However, in higher magnetic fields, closer to the field-tuned quantum phase transition, subtle deviations from this semiclassical behavior are observed, which are consistent with expectations of quantum fluctuations. Although the phase transition is driven by the local 4 f degrees of freedom, the crystal lattice still plays a crucial role, both in terms of mediating the interactions between the local quadrupoles and in determining the critical scaling exponents, even though the phase transition itself can be described via mean field. In particular, bilinear coupling of the nematic order parameter to acoustic phonons changes the spatial and temporal fluctuations of the former in a fundamental way, resulting in different critical behavior of the nematic transverse-field Ising model, as compared to the usual case of the magnetic transverse-field Ising model. Our results establish TmVO 4 as a model material and electronic nematicity as a paradigmatic example for quantum criticality in insulators.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Assignment of structural transitions during mechanical unwrapping of nucleosomes and their disassembly products

Nucleosome DNA unwrapping and its disassembly into hexasomes and tetrasomes is necessary for genomic access and plays an important role in transcription regulation. Previous single-molecule mechanical nucleosome unwrapping revealed a low- and a high-force transitions, and force-FRET pulling experiments showed that DNA unwrapping is asymmetric, occurring always first from one side before the other. However, the assignment of DNA segments involved in these transitions remains controversial. Here, using high-resolution optical tweezers with simultaneous single-molecule FRET detection, we show that the low-force transition corresponds to the undoing of the outer wrap of one side of the nucleosome (∼27 bp), a process that can occur either cooperatively or noncooperatively, whereas the high-force transition corresponds to the simultaneous unwrapping of ∼76 bp from both sides. This process may give rise stochastically to the disassembly of nucleosomes into hexasomes and tetrasomes whose unwrapping/rewrapping trajectories we establish. In contrast, nucleosome rewrapping does not exhibit asymmetry. To rationalize all previous nucleosome unwrapping experiments, it is necessary to invoke that mechanical unwrapping involves two nucleosome reorientations: one that contributes to the change in extension at the low-force transition and another that coincides but does not contribute to the high-force transition.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

Multi-band, multi-epoch observations of the transiting warm Jupiter WASP-80b

WASP-80b is a warm Jupiter transiting a bright late-K/early-M dwarf, providing a good opportunity to extend the atmospheric study of hot Jupiters toward the lower temperature regime. We report multi-band, multi-epoch transit observations of WASP-80b by using three ground-based telescopes covering from optical (g', R{sub c}, and I{sub c} bands) to near-infrared (NIR; J, H, and K{sub s} bands) wavelengths. We observe 5 primary transits, each in 3 or 4 different bands simultaneously, obtaining 17 independent transit light curves. Combining them with results from previous works, we find that the observed transmission spectrum is largely consistent with both a solar abundance and thick cloud atmospheric models at a 1.7σ discrepancy level. On the other hand, we find a marginal spectral rise in the optical region compared to the NIR region at the 2.9σ level, which possibly indicates the existence of haze in the atmosphere. We simulate theoretical transmission spectra for a solar abundance but hazy atmosphere, finding that a model with equilibrium temperature of 600 K can explain the observed data well, having a discrepancy level of 1.0σ. We also search for transit timing variations, but find no timing excess larger than 50 s from a linear ephemeris. In addition, we conduct 43 day long photometric monitoring of the host star in the optical bands, finding no significant variation in the stellar brightness. Combined with the fact that no spot-crossing event is observed in the five transits, our results confirm previous findings that the host star appears quiet for spot activities, despite the indications of strong chromospheric activities.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

The effects of refraction on transit transmission spectroscopy: application to Earth-like exoplanets

We quantify the effects of refraction in transit transmission spectroscopy on spectral absorption features and on temporal variations that could be used to obtain altitude-dependent spectra for planets orbiting stars of different stellar types. We validate our model against altitude-dependent transmission spectra of the Earth from ATMOS and against lunar eclipse spectra from Pallé et al. We perform detectability studies to show the potential effects of refraction on hypothetical observations of Earth analogs with the James Webb Space Telescope NIRSPEC. Due to refraction, there will be a maximum tangent pressure level that can be probed during transit for each given planet-star system. We show that because of refraction, for an Earth-analog planet orbiting in the habitable zone of a Sun-like star only the top 0.3 bars of the atmosphere can be probed, leading to a decrease in the signal-to-noise ratio (S/N) of absorption features by 60%, while for an Earth-analog planet orbiting in the habitable zone of an M5V star it is possible to probe almost the entire atmosphere with minimal decreases in S/N. We also show that refraction can result in temporal variations in the transit transmission spectrum which may provide a way to obtain altitude-dependent spectra of exoplanet atmospheres. Additionally, the variations prior to ingress and subsequent to egress provide a way to probe pressures greater than the maximum tangent pressure that can be probed during transit. Therefore, probing the maximum range of atmospheric altitudes, and in particular the near-surface environment of an Earth-analog exoplanet, will require looking at out-of-transit refracted light in addition to the in-transit spectrum.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Strong brightness variations signal cloudy-to-clear transition of brown dwarfs

We report the results of a J-band search for cloud-related variability in the atmospheres of 62 L4-T9 dwarfs using the Du Pont 2.5 m telescope at Las Campanas Observatory and the Canada-France-Hawaii Telescope on Mauna Kea. We find 9 of 57 objects included in our final analysis to be significantly variable with >99% confidence, 5 of which are new discoveries. In our study, strong signals (peak-to-peak amplitudes >2%) are confined to the L/T transition (4/16 objects with L9-T3.5 spectral types and 0/41 objects for all other spectral types). The probability that the observed occurrence rates for strong variability inside and outside the L/T transition originate from the same underlying true occurrence rate is excluded at >99.7% confidence. Based on a careful assessment of our sensitivity to astrophysical signals, we infer that 39{sub −14}{sup +16}% of L9-T3.5 dwarfs are strong variables on rotational timescales. If we consider only L9-T3.5 dwarfs with 0.8 < J – K {sub s} < 1.5, and assume an isotropic distribution of spin axes for our targets, we find that 80{sub −19}{sup +18}% would be strong variables if viewed edge-on; azimuthal symmetry and/or binarity may account for non-variable objects in this group. These observations suggest that the settling of condensate clouds below the photosphere in brown dwarf (BD) atmospheres does not occur in a spatially uniform manner. Rather, the formation and sedimentation of dust grains at the L/T transition is coupled to atmospheric dynamics, resulting in highly contrasting regions of thick and thin clouds and/or clearings. Outside the L/T transition we identify five weak variables (peak-to-peak amplitudes of 0.6%-1.6%). Excluding L9-T3.5 spectral types, we infer that 60{sub −18}{sup +22}% of targets vary with amplitudes of 0.5%-1.6%, suggesting that surface heterogeneities are common among L and T dwarfs. Our survey establishes a significant link between strong variability and L/T transition spectral types, providing evidence in support of the hypothesis that cloud holes contribute to the abrupt decline in condensate opacity and 1 μm brightening observed in this regime. More generally, fractional cloud coverage is an important model parameter for BDs and giant planets, especially those with L/T transition spectral types and colors.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Obliquities of Kepler stars: comparison of single- and multiple-transit systems

The stellar obliquity of a transiting planetary system can be constrained by combining measurements of the star's rotation period, radius, and projected rotational velocity. Here, we present a hierarchical Bayesian technique for recovering the obliquity distribution of a population of transiting planetary systems and apply it to a sample of 70 Kepler objects of interest. With ≈95% confidence, we find that the obliquities of stars with only a single detected transiting planet are systematically larger than those with multiple detected transiting planets. This suggests that a substantial fraction of Kepler's single-transiting systems represent dynamically hotter, less orderly systems than the 'pancake-flat' multiple-transiting systems.

79 ASTRONOMY AND ASTROPHYSICS↗