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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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Bottom-up coarse-grained models that accurately describe the structure, pressure, and compressibility of molecular liquids

The present work investigates the capability of bottom-up coarse-graining (CG) methods for accurately modeling both structural and thermodynamic properties of all-atom (AA) models for molecular liquids. In particular, we consider 1, 2, and 3-site CG models for heptane, as well as 1 and 3-site CG models for toluene. For each model, we employ the multiscale coarse-graining method to determine interaction potentials that optimally approximate the configuration dependence of the many-body potential of mean force (PMF). We employ a previously developed “pressure-matching” variational principle to determine a volume-dependent contribution to the potential, U{sub V}(V), that approximates the volume-dependence of the PMF. We demonstrate that the resulting CG models describe AA density fluctuations with qualitative, but not quantitative, accuracy. Accordingly, we develop a self-consistent approach for further optimizing U{sub V}, such that the CG models accurately reproduce the equilibrium density, compressibility, and average pressure of the AA models, although the CG models still significantly underestimate the atomic pressure fluctuations. Additionally, by comparing this array of models that accurately describe the structure and thermodynamic pressure of heptane and toluene at a range of different resolutions, we investigate the impact of bottom-up coarse-graining upon thermodynamic properties. In particular, we demonstrate that U{sub V} accounts for the reduced cohesion in the CG models. Finally, we observe that bottom-up coarse-graining introduces subtle correlations between the resolution, the cohesive energy density, and the “simplicity” of the model.

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

X-point position dependence of edge intrinsic toroidal rotation on the Tokamak à Configuration Variable

Recent theoretical work predicts intrinsic toroidal rotation in the tokamak edge to depend strongly on the normalized major radial position of the X-point. With this motivation, we conducted a series of Ohmic L-mode shots on the Tokamak à Configuration Variable, moving the X-point from the inboard to the outboard edge of the last closed flux surface in both lower and upper single null configurations. The edge toroidal rotation evolved from strongly co-current for an inboard X-point to either vanishing or counter-current for an outboard X-point, in agreement with the theoretical expectations. The whole rotation profile shifted roughly rigidly with the edge rotation, resulting in variation of the peak core rotation by more than a factor of two. Core rotation reversals had little effect on the edge rotation. Edge rotation was slightly more counter-current for unfavorable than favorable ∇B drift discharges.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Position dependent optical coupling between single quantum dots and photonic crystal nanocavities

We demonstrate precise and quick detection of the positions of quantum dots (QDs) embedded in two-dimensional photonic crystal nanocavities. We apply this technique to investigate the QD position dependence of the optical coupling between the QD and the nanocavity. We use a scanning electron microscope (SEM) operating at a low acceleration voltage to detect surface bumps induced by the QDs buried underneath. This enables QD detection with a sub-10 nm precision. We then experimentally measure the vacuum Rabi spectra to extract the optical coupling strengths (gs) between single QDs and cavities, and compare them to the values estimated by a combination of the SEM-measured QD positions and electromagnetic cavity field simulations. We found a highly linear relationship between the local cavity field intensities and the QD-cavity gs, suggesting the validity of the point dipole approximation used in the estimation of the gs. The estimation using SEM has a small standard deviation of ±6.2%, which potentially enables the high accuracy prediction of g prior to optical measurements. Our technique will play a key role for deeply understanding the interaction between QDs and photonic nanostructures and for advancing QD-based cavity quantum electrodynamics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Structural anisotropic properties of a-plane GaN epilayers grown on r-plane sapphire by molecular beam epitaxy

Heteroepitaxial non-polar III-Nitride layers may exhibit extensive anisotropy in the surface morphology and the epilayer microstructure along distinct in-plane directions. The structural anisotropy, evidenced by the “M”-shape dependence of the (112{sup ¯}0) x-ray rocking curve widths on the beam azimuth angle, was studied by combining transmission electron microscopy observations, Raman spectroscopy, high resolution x-ray diffraction, and atomic force microscopy in a-plane GaN epilayers grown on r-plane sapphire substrates by plasma-assisted molecular beam epitaxy (PAMBE). The structural anisotropic behavior was attributed quantitatively to the high dislocation densities, particularly the Frank-Shockley partial dislocations that delimit the I{sub 1} intrinsic basal stacking faults, and to the concomitant plastic strain relaxation. On the other hand, isotropic samples exhibited lower dislocation densities and a biaxial residual stress state. For PAMBE growth, the anisotropy was correlated to N-rich (or Ga-poor) conditions on the surface during growth, that result in formation of asymmetric a-plane GaN grains elongated along the c-axis. Such conditions enhance the anisotropy of gallium diffusion on the surface and reduce the GaN nucleation rate.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Large-amplitude Longitudinal Oscillations in a Solar Filament

In this paper, we report our multiwavelength observations of the large-amplitude longitudinal oscillations of a filament observed on 2015 May 3. Located next to active region 12335, the sigmoidal filament was observed by the ground-based H α telescopes from the Global Oscillation Network Group and by the Atmospheric Imaging Assembly instrument on board the Solar Dynamics Observatory . The filament oscillations were most probably triggered by the magnetic reconnection in the filament channel, which is characterized by the bidirectional flows, brightenings in EUV and soft X-ray, and magnetic cancellation in the photosphere. The directions of oscillations have angles of 4°–36° with respect to the filament axis. The whole filament did not oscillate in phase as a rigid body. Meanwhile, the oscillation periods (3100–4400 s) have a spatial dependence, implying that the curvature radii ( R ) of the magnetic dips are different at different positions. The values of R are estimated to be 69.4–133.9 Mm, and the minimum transverse magnetic field of the dips is estimated to be 15 G. The amplitudes of S5-S8 grew with time, while the amplitudes of S9-S14 damped with time. The oscillation amplitudes range from a few to ten Mm, and the maximum velocity can reach 30 km s{sup −1}. Interestingly, the filament experienced mass drainage southward at a speed of ∼27 km s{sup −1}. The oscillations continued after the mass drainage and lasted for more than 11 hr. After the mass drainage, the oscillation phases did not change much. The periods of S5-S8 decreased, while the periods of S9-S14 increased. The amplitudes of S5-S8 damped with time, while the amplitudes of S9-S14 grew. Most of the damping (growing) ratios are between −9 and 14. We offer a schematic cartoon to explain the complex behaviors of oscillations by introducing thread-thread interaction.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

The Pointing Self-calibration Algorithm for Aperture Synthesis Radio Telescopes

This paper is concerned with algorithms for calibration of direction-dependent effects (DDE) in aperture synthesis radio telescopes (ASRT). After correction of direction-independent effects (DIE) using self-calibration, imaging performance can be limited by the imprecise knowledge of the forward gain of the elements in the array. In general, the forward gain pattern is directionally dependent and varies with time due to a number of reasons. Some factors, such as rotation of the primary beam with Parallactic Angle for Azimuth–Elevation mount antennas are known a priori. Some, such as antenna pointing errors and structural deformation/projection effects for aperture-array elements cannot be measured a priori. Thus, in addition to algorithms to correct for DD effects known a priori, algorithms to solve for DD gains are required for high dynamic range imaging. Here, we discuss a mathematical framework for antenna-based DDE calibration algorithms and show that this framework leads to computationally efficient optimal algorithms that scale well in a parallel computing environment. As an example of an antenna-based DD calibration algorithm, we demonstrate the Pointing SelfCal (PSC) algorithm to solve for the antenna pointing errors. Our analysis show that the sensitivity of modern ASRT is sufficient to solve for antenna pointing errors and other DD effects. We also discuss the use of the PSC algorithm in real-time calibration systems and extensions for antenna Shape SelfCal algorithm for real-time tracking and corrections for pointing offsets and changes in antenna shape.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2004

CNS development under altered gravity: cerebellar glial and neuronal protein expression in rat neonates exposed to hypergravity

The future of space exploration depends on a solid understanding of the developmental process under microgravity, specifically in relation to the central nervous system (CNS). We have previously employed a hypergravity paradigm to assess the impact of altered gravity on the developing rat cerebellum. The present study addresses the molecular mechanisms involved in the cerebellar response to hypergravity. Specifically, the study focuses on the expression of selected glial and neuronal cerebellar proteins in rat neonates exposed to hypergravity (1.5 G) from embryonic day (E)11 to postnatal day (P)6 or P9 (the time of maximal cerebellar changes) comparing them against their expression in rat neonates developing under normal gravity. Proteins were analyzed by quantitative Western blots of cerebellar homogenates; RNA analysis was performed in the same samples using quantitative PCR. Densitometric analysis of Western blots suggested a reduction in glial (glial acidic protein, GFAP) and neuronal (neuronal cell adhesion molecule, NCAM-L1, synaptophysin) proteins, but the changes in individual cerebellar proteins in hypergravity-exposed neonates appeared both age- and gender-specific. RNA analysis suggested a reduction in GFAP and synaptophysin mRNAs on P6. These data suggest that exposure to hypergravity may interfere with the expression of selected cerebellar proteins. These changes in protein expression may be involved in mediating the effect of hypergravity on the developing rat cerebellum. c2003 COSPAR. Published by Elsevier Ltd. All rights reserved.

NASA Program Fundamental Space Biology↗
DOE OSTI2015

Interference between Coulombic and CT-mediated couplings in molecular aggregates: H- to J-aggregate transformation in perylene-based π-stacks

The spectroscopic differences between J and H-aggregates are traditionally attributed to the spatial dependence of the Coulombic coupling, as originally proposed by Kasha. However, in tightly packed molecular aggregates wave functions on neighboring molecules overlap, leading to an additional charge transfer (CT) mediated exciton coupling with a vastly different spatial dependence. The latter is governed by the nodal patterns of the molecular LUMOs and HOMOs from which the electron (t{sub e}) and hole (t{sub h}) transfer integrals derive. The sign of the CT-mediated coupling depends on the sign of the product t{sub e}t{sub h} and is therefore highly sensitive to small (sub-Angstrom) transverse displacements or slips. Given that Coulombic and CT-mediated couplings exist simultaneously in tightly packed molecular systems, the interference between the two must be considered when defining J and H-aggregates. Generally, such π-stacked aggregates do not abide by the traditional classification scheme of Kasha: for example, even when the Coulomb coupling is strong the presence of a similarly strong but destructively interfering CT-mediated coupling results in “null-aggregates” which spectroscopically resemble uncoupled molecules. Based on a Frenkel/CT Holstein Hamiltonian that takes into account both sources of electronic coupling as well as intramolecular vibrations, vibronic spectral signatures are developed for integrated Frenkel/CT systems in both the perturbative and resonance regimes. In the perturbative regime, the sign of the lowest exciton band curvature, which rigorously defines J and H-aggregation, is directly tracked by the ratio of the first two vibronic peak intensities. Even in the resonance regime, the vibronic ratio remains a useful tool to evaluate the J or H nature of the system. The theory developed is applied to the reversible H to J-aggregate transformations recently observed in several perylene bisimide systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Heliospheric influence on the anisotropy of TeV cosmic rays

This paper provides a theory of using Liouville's theorem to map the anisotropy of TeV cosmic rays seen at Earth using the particle distribution function in the local interstellar medium (LISM). The ultimate source of cosmic ray anisotropy is the energy, pitch angle, and spatial dependence of the cosmic ray distribution function in the LISM. Because young nearby cosmic ray sources can make a special contribution to the cosmic ray anisotropy, the anisotropy depends on the source age, distance and magnetic connection, and particle diffusion of these cosmic rays, all of which make the anisotropy sensitive to the particle energy. When mapped through the magnetic and electric field of a magnetohydrodynamic model heliosphere, the large-scale dipolar and bidirectional interstellar anisotropy patterns become distorted if they are seen from Earth, resulting in many small structures in the observations. Best fits to cosmic ray anisotropy measurements have allowed us to estimate the particle density gradient and pitch angle anisotropies in the LISM. It is found that the heliotail, hydrogen deflection plane, and the plane perpendicular to the LISM magnetic field play a special role in distorting cosmic ray anisotropy. These features can lead to an accurate determination of the LISM magnetic field direction and polarity. The effects of solar cycle variation, the Sun's coronal magnetic field, and turbulence in the LISM and heliospheric magnetic fields are minor but clearly visible at a level roughly equal to a fraction of the overall anisotropy amplitude. The heliospheric influence becomes stronger at lower energies. Below 1 TeV, the anisotropy is dominated by small-scale patterns produced by disturbances in the heliosphere.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

MONK10: Burnup credit capability - 14596

MONK{sup R} is a Monte Carlo code for nuclear criticality and reactor physics analyses. It has a proven track record of application to the whole of the nuclear fuel cycle and is well established in the UK criticality community. Furthermore it is increasingly being used for reactor physics analysis (as described at ICNC 2011), which makes it an ideal tool for burn-up credit (BUC) calculations. Throughout the paper, example calculations based on a PWR are presented to illustrate the capabilities of the MONK10 code. In order to account for the spatial dependence of material burn-up it has in the past been necessary to design models with multiple regions and materials specifically to allow material burn-up to vary spatially. This is very labour intensive and difficult to change at a later stage. A new code version, MONK10, was released last year which includes the facility to allow a burn-up (BU) mesh to be superimposed on an existing model in order to account for the spatial dependence of the burn-up. This facility is used to consider the effect of radial position of a fuel element in a PWR core on BUC. Additionally, a thermal hydraulics (TH) mesh can be used to specify region dependent temperature. This, coupled with the fact that MONK10 also incorporates an on-the-fly Doppler broadening methodology facilitates the modelling of spatially dependent temperatures for the different components. A TH mesh is used to superimpose a temperature profile on a PWR based model and the effect of this on BUC is considered. The burn-up modelling in MONK has been benchmarked against the ANSWERS WIMS deterministic reactor physics code. Once the burn-up calculation has been completed and the depleted fuel compositions determined the spent fuel compositions can be transferred into a model of a storage facility or transport flask in order to perform burn-up credit analysis. The initial model is usually described as the donor model and the latter model as the receiver model. This transfer is carried out using the COWL option which allows the specification of a material in the receiver model based on the material's composition in a given BU mesh cell from the donor model. This allows compositions and densities to be transferred and also allows user specified adjustments to be made. For example, this could include omitting the fission products in order to estimate their contribution to burn-up credit and provide an actinide-only analysis. The effect of excluding appropriate nuclides is presented. An example of how the ANSWERS SPRUCE code can be used to quantify uncertainty in a BUC calculation is also presented. (authors)

42 ENGINEERING↗
NASA NTRS2006

Autonomic Management of Space Missions

With NASA s renewed commitment to outer space exploration, greater emphasis is being placed on both human and robotic exploration. Even when humans are involved in the exploration, human tending of assets becomes cost-prohibitive or in many cases is simply not feasible. In addition, certain exploration missions will require spacecraft that will be capable of venturing where humans cannot be sent. Early space missions were operated manually from ground control centers with little or no automated operations. In the mid-l980s, the high costs of satellite operations prompted NASA, and others, to begin automating as many functions as possible. In our context, a system is autonomous if it can achieve its goals without human intervention. A number of more-or-less automated ground systems exist today, but work continues with the goal being to reduce operations costs to even lower levels. Cost reductions can be achieved in a number of areas. Ground control and spacecraft operations are two such areas where greater autonomy can reduce costs. As a consequence, autonomy is increasingly seen as a critical approach for robotic missions and for some aspects of manned missions. Although autonomy will be critical for the success of future missions (and indeed will enable certain kinds of science data gathering approaches), missions imbued with autonomy must also exhibit autonomic properties. Exploitation of autonomy alone, without emphasis on autonomic properties, will leave spacecraft vulnerable to the dangerous environments in which they must operate. Without autonomic properties, a spacecraft may be unable to recognize negative environmental effects on its components and subsystems, or may be unable to take any action to ameliorate the effects. The spacecraft, though operating autonomously, may then sustain a degradation of performance of components or subsystems, and consequently may have a reduced potential for achieving mission objectives. In extreme cases, lack of autonomic properties could leave the spacecraft unable to recover from faults. Ensuring that exploration spacecraft have autonomic properties will increase the survivability and therefore the likelihood of success of these missions. In fact, over time, as mission requirements increased demands on spacecraft capabilities and longevity, designers have gradually built more autonomicity into spacecraft. For example, a spacecraft in low-earth orbit may experience an out-of-bounds perturbation of its attitude (orientation) due to increased drag caused by increased atmospheric density at its altitude as a result of a sufficiently large solar flare. If the spacecraft was designed to recognize the excessive attitude perturbation, it could decide to protect itself by going into a safe-hold mode where its internal configuration and operation are altered to conserve power and its coarse attitude is adjusted to point its solar panels toward the Sun to maximize power generation. This is an example of a simple type of autonomic behavior that has actually occurred. Future mission concepts will be increasingly dependent on space system survivability enabled by more advanced types of autonomic behaviors

Hinchey, Michael G.↗
DOE OSTI2016

Two Photon Absorption Laser Induced Fluorescence for Neutral Hydrogen Profile Measurements

The magnitude and spatial dependence of neutral density in magnetic confinement fusion experiments is a key physical parameter, particularly in the plasma edge. Modeling codes require precise measurements of the neutral density to calculate charge-exchange power losses and drag forces on rotating plasmas. However, direct measurements of the neutral density are problematic. In this work, we proposed to construct a laser-based diagnostic capable of providing spatially resolved measurements of the neutral density in the edge of plasma in the DIII-D tokamak. The diagnostic concept is based on two-photon absorption laser induced fluorescence (TALIF). By injecting two beams of 205 nm light (co or counter propagating), ground state hydrogen (or deuterium or tritium) can be excited from the n = 1 level to the n = 3 level at the location where the two beams intersect. Individually, the beams experience no absorption, and therefore have no difficulty penetrating even dense plasmas. After excitation, a fraction of the hydrogen atoms decay from the n = 3 level to the n = 2 level and emit photons at 656 nm (the H α line). Calculations based on the results of previous TALIF experiments in magnetic fusion devices indicated that a laser pulse energy of approximately 3 mJ delivered in 5 ns would provide sufficient signal-to-noise for detection of the fluorescence. In collaboration with the DIII-D engineering staff and experts in plasma edge diagnostics for DIII-D from Oak Ridge National Laboratory (ORNL), WVU researchers designed a TALIF system capable of providing spatially resolved measurements of neutral deuterium densities in the DIII-D edge plasma. The laser systems were specified, purchased, and assembled at WVU. The TALIF system was tested on a low-power hydrogen discharge at WVU and the plan was to move the instrument to DIII-D for installation in collaboration with ORNL researchers. After budget cuts at DIII-D, the DIII-D facility declined to support installation on their tokamak. Instead, after a no-cost extension, the apparatus was moved to the University of Washington-Seattle and successfully tested on the HIT-SI3 spheromak experiment. As a result of this project, TALIF measurements of the absolutely calibrated neutral density hydrogen and deuterium were obtained in a helicon source and in a spheromak, designs were developed for installation of a TALIF system on a tokamak, and a new, xenon-based calibration scheme was proposed and demonstrated. The xenon-calibration scheme eliminates significant problems that were identified with the standard krypton calibration scheme.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Range‐separated density functional theory using multiresolution analysis and quantum computing

Quantum computers are expected to outperform classical computers for specific problems in quantum chemistry. Such calculations remain expensive, but costs can be lowered through the partition of the molecular system. In the present study, partition was achieved with range-separated density functional theory (RS-DFT). The use of RS-DFT reduces both the basis set size and the active space size dependence of the ground state energy in comparison with the use of wave function theory (WFT) alone. The utilization of pair natural orbitals (PNOs) in place of canonical molecular orbitals (MOs) results in more compact qubit Hamiltonians. To test this strategy, a basis-set independent framework, known as multiresolution analysis (MRA), was employed to generate PNOs. Tests were conducted with the variational quantum eigensolver for a number of molecules. The results show that the proposed approach reduces the number of qubits needed to reach a target energy accuracy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Numerical simulations of chaotic and complex spatiotemporal patterns in fractional reaction–diffusion systems

The generalized fractional reaction–diffusion equations which exist in the form of noninteger order partial differential equations have now found wide application for illustrating important and useful physical phenomena, such as subdiffusive and superdiffusive scenarios. The space fractional derivatives are defined in the Riesz sense on the intervals 0 < α < 1 and 1 < α ≤ 2. We propose robust numerical techniques, such as a spectral representation of the fractional Laplacian operator in conjunction with the exponential time differencing method, and present the equivalent relationship between the Riesz fractional derivative and fractional Laplacian operator. We apply these techniques to numerically solve a range of chaotic processes, such as the Chua’s equations, Rössler system, Lorenz and Lorenz-type systems. Simulation results revealed various complex and spatiotemporal chaos, spiral chaos, intermittent chaos and spots patterns in two-dimensional space fractional reaction–diffusion problems.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2017

Casimir–Polder energy for axially symmetric systems

We develop a formalism suitable for studying Maxwell’s equations in the presence of a medium that is axially symmetric, in particular with respect to Casimir–Polder interaction energies. As an application, we derive the Casimir–Polder interaction energy between an electric δ-function plate and an anisotropically polarizable molecule for arbitrary orientations of the principal axes of polarizabilities of the molecule. We show that in the perfect conductor limit for the plate the interaction is insensitive to the orientation of the polarizabilities of the molecule. We obtain the Casimir–Polder energy between an electric δ-function sphere and an anisotropically polarizable molecule, again for arbitrary orientations of the principal axes of polarizabilities of the molecule. We derive results when the polarizable molecule is either outside the sphere, or inside the sphere. We present the perfectly conducting limit for the δ-function sphere, and also the interaction energy for the special case when the molecule is at the center of the sphere. Our general proposition is that the Casimir–Polder energy between a dielectric body with axial symmetry and a unidirectionally polarizable molecule placed on the axis with its polarizability parallel to the axis gets non-zero contribution only from the m=0 azimuth mode. This feature in conjunction with the property that the m=0 mode separates into transverse electric and transverse magnetic modes allows the evaluation of Casimir–Polder energies for axially symmetric systems in a relatively easy manner.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

The association between exposure to environmental factors and the occurrence of attention-deficit/hyperactivity disorder (ADHD). A population-based retrospective cohort study

Highlights: • We found a certain north-south pattern for the risk of occurrence of ADHD. • These clusters could be related to some of the environmental variables. • In particular, an increased risk of occurrence of ADHD was found. • Living less than 100 m from an agricultural area or a residential Street. • Living less than 300 m from a motorway/dual carriageway or an industrial estate. A number of factors contribute to attention deficit hyperactivity disorder (ADHD) and although they are not fully known, the occurrence of ADHD seems to be a consequence of an interaction between multiple genetic and environmental factors. However, apart from pesticides, the evidence is inadequate and inconsistent as it differs not only in the population and time period analysed, but also in the type of study, the control of the confounding variables and the statistical methods used. In the latter case, the studies also differ in the adjustment of spatial and temporal variability. Our objective here, is to provide evidence on an association between environmental factors and ADHD.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Light-activated interlayer contraction in two-dimensional perovskites for high-efficiency solar cells

Understanding and tailoring the physical behaviour of halide perovskites under practical environments is critical for designing efficient and durable optoelectronic devices. Here, we report that continuous light illumination leads to >1% contraction in the out-of-plane direction in two-dimensional hybrid perovskites, which is reversible and strongly dependent on the specific superlattice packing. X-ray photoelectron spectroscopy measurements show that constant light illumination results in the accumulation of positive charges in the terminal iodine atoms, thereby enhancing the bonding character of inter-slab I–I interactions across the organic barrier and activating out-of-plane contraction. Correlated charge transport, structural and photovoltaic measurements confirm that the onset of the light-induced contraction is synchronized to a threefold increase in carrier mobility and conductivity, which is consistent with an increase in the electronic band dispersion predicted by first-principles calculations. Flux-dependent space-charge-limited current measurement reveals that light-induced interlayer contraction activates interlayer charge transport. Lastly, the enhanced charge transport boosts the photovoltaic efficiency of two-dimensional perovskite solar cells up to 18.3% by increasing the device’s fill factor and open-circuit voltage.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Swelling Inhibition of Liquid Crystalline Colloidal Montmorillonite and Beidellite Clays by DNA

Exploring the interaction of nucleic acids with clay minerals is important to understand such issues as the persistence in soils of biomolecules and the appearance of genetic polymers in prebiotic environments. Colloidal dispersions of double stranded DNA and clay nanosheets may also provide interesting model systems to study the statistical physics of mixtures of semi-flexible rods and plates. Here, we show that adding very small amounts of DNA to liquid-crystalline montmorillonite and beidellite smectite clay suspensions strongly widens the isotropic/nematic phase coexistence region. Moreover, a spectroscopic study shows that, upon DNA addition, the first DNA molecules adsorb onto the clay particles. Remarkably, synchrotron small-angle X-ray scattering experiments reveal that the average distance between the clay sheets, in the nematic phase at coexistence, decreases with increasing DNA concentration and that the inhibition of swelling by DNA becomes almost independent of clay concentration. We interpret this DNA-mediated attraction between clay nanosheets by bridging conformations of DNA strands (plates on a string structure). In addition to bridging, DNA chains can form "loops" between sections adsorbed on the same particle, giving rise to sheet repulsions due to protruding loops. Furthermore, this interpretation agrees with the observed inter-clay spacings being dependent only on the DNA concentration.

59 BASIC BIOLOGICAL SCIENCES↗