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At least 271 records · Page 15

Renewal: Coherent control of spin states in organic electronics – discovery and investigation of complex room-temperature magnetic quantum excitations

In the course of four funding cycles of this project, its research focused on the exploration and understanding of spin-dependent electronic processes in organic semiconductors. It aimed to investigate the potential of harnessing the spin degree of freedom in organic materials for various applications such as spin electronics, quantum information, sensors, and as well as quantum coherent spin phenomena of charge carrier states in organic semiconductors, with the aim to develop room-temperature-based quantum applications. Specifically, the project aimed to: Apply new diagnostic tools, i.e. spin spectroscopy techniques, for paramagnetic charge carrier states in organic semiconductors, based on coherent control with pulsed electron spin resonance to understand spin relaxation and spin mixing mechanisms in organic semiconductor materials and devices such as OLEDs. Explore the nature of charge carrier spin-coupling and pathways for its manipulation to control the physical behaviors of these materials. This involves investigating spin interactions through materials structure, composition, morphological dependencies, isotopic effects, and externally applied electric and magnetic fields, with the goal to manipulate electrical and optical material properties by adjusting spin-orbit, spin-dipolar, spin-exchange, as well as spin-hyperfine interactions to open up this materials class for new applications. Study spin-dependent charge carrier transport and recombination and how these observables are governed by spin-propagation, especially coherent spin propagation as well as collective spin-effects such as the spin-Dicke effect and resonant multi-photon magnetic dipole transitions. The project utilized pulsed electrically detected magnetic resonance (pEDMR) and pulsed optically detected magnetic resonance (pODMR) techniques over a wide frequency range. These techniques enabled the observation and quantification of various spin-spin coupling types, including spin-exchange, spin-dipolar, hyperfine, and spin-orbit interactions. The project will leverage low- to mid-frequency pEDMR/pODMR facilities and collaboration with the National High Magnetic Field Laboratory.

36 MATERIALS SCIENCE↗

Building a spontaneously formed and self-healing protective layer with an F-rich electrochemically active organic molecule for ultra-stable Li metal batteries

Additives in the electrolyte act as engineers in Li metal batteries. Inspired by the superior cycle performance of organic materials in half cells, tetrafluoro-1,4-benzoquinone (TFBQ), the main structure of which has been widely applied as an organic cathode material, is utilized for the first time as an additive for Li metal protection. By chemical and electrochemical reactions between TFBQ and the Li metal surface, an F-rich interface layer is in situ formed on the Li metal surface during the charge and discharge process. From electrochemical tests and characterization, the powerful self-healing ability of the interface layer enabled by TFBQ is revealed, making an extremely stable Li metal anode. By using a lean electrolyte with 0.1 M TFBQ, the cycle life of Li|Li symmetric cells is increased at least 6 times compared to the control group. Moreover, impressive full cell performance was achieved. Ultra-stable Li–LFP cells showed a 0.026% average degradation for 600 cycles at 1C and Li–NMC622 cells showed a 36.8% higher capacity compared to the control group over 200 cycles at 0.5C, which are among the best results reported. Furthermore, this work efficiently and conveniently provides a new research direction to Li metal protection and Li metal batteries.

25 ENERGY STORAGE↗

Layered structures of assembled imine-linked macrocycles and two-dimensional covalent organic frameworks give rise to prolonged exciton lifetimes

Ordered organic materials and assemblies have great potential to be tailored to have desirable properties for optoelectronic applications, such as long exciton lifetime and high directional exciton mobility. Framework materials, such as two-dimensional covalent organic frameworks (2D COFs), as well as their truncated macrocyclic analogues, are versatile platforms to organize functional aromatic systems into designed assemblies and robust materials. In this study we investigate the exciton dynamics in a 2D COF, its corresponding hexagonal macrocycle, and extended nanotubes comprised of stacked macrocycles. The excitonic behavior of these three systems provide an understanding of excitonic processes that occur in the plane of the covalently bonded 2D macromolecules and between layers of the nanotubes and 2D COF. The nanotube and analogous 2D COF exhibit longer excited-state lifetimes (~100 ps) compared to the individual, solvated macrocycles (<0.5 ps). These differences are attributed to the internal conversion facilitated by the internal motions of the imine linkages which are significantly reduced in the assembled macrocycles in the nanotube and 2D COF sheets in the layered structures. The exciton diffusion processes in the assembled nanotubes and 2D COF systems were characterized by the autocorrelations of the transition dipole moment of the excitons, giving the depolarization time constants for both systems to be ~1 ps. This work also reveals the anisotropic exciton dynamics related to the in-plane and inter-plane structural factors in these systems. These studies provide guidance for the design of future COF materials, where the longer excited state lifetimes imparted by assembly are beneficial for optoelectronic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrocarbons on Saturns Satellites: Relationship to Interstellar Dust and the Solar Nebula

To understand the origin and evolution of our Solar System, and the basic components that led to life on Earth, we study interstellar and planetary spectroscopic signatures. The possible relationship of organic material detected in carbonaceous meteorites, interplanetary dust particles (IDPs), comets and the interstellar medium have been the source of speculation over the years as the composition and processes that governed the early solar nebula have been explored to understand the extent to which primitive material survived or became processed. The Cassini VIMS has provided new data relevant to this problem. Three of Saturn's satellites, Phoebe, Iapetus, and Hyperion, are found to have aromatic and aliphatic hydrocarbons on their surfaces. The aromatic hydrocarbon signature (C-H stretching mode at 3.28 micrometers) is proportionally significantly stronger (relative to the aliphatic bands) than that seen in other Solar System bodies (e.g., comets) and materials (Stardust samples, IDPs, meteorites) and the distinctive sub-features of the 3.4 micrometer aliphatic band (CH2 and CH3 groups) are reminiscent of those widely detected throughout the diffuse ISM. Phoebe may be a captured object that originated in the region beyond the present orbit of Neptune, where the solar nebula contained a large fraction of original interstellar ice and dust that was less processed than material closer to the Sun. Debris from Phoebe now resident on Iapetus and Hyperion, as well as o Phoebe itself, thus presents a unique blend of hydrocarbons, amenable to comparisons with interstellar hydrocarbons and other Solar System materials. The dust ring surrounding Saturn, in which Phoebe is embedded, probably originated from a collision with Phoebe. Dust ring particles are the likely source of the organic-bearing materials, and perhaps the recently identified small particles of Fe detected on Saturn's satellites. Lab measurements of the absolute band strengths of representative aliphatic and aromatic molecules, together with measurements from the VIMS data, allow us to calculate the number of C atoms to find the relative abundances of C atoms in the two kinds of organic molecules. The strength of the prominent aromatic C-H stretch band relative to the aliphatic band complex in Phoebe and Iapetus indicates that the relative abundance of aromatic to aliphatic carbon is very large (greater than 200). In contract, the aromatic band is nearly imperceptible in spectra of interplanetary dust particles (IDP), returned samples from comet 91P/Wild 2, insoluable carbonaceous material in most meteorites, and the diffuse interstellar dust (DISM) (although aromatics are known in all these materials-here we consider only the spectroscopic signature)

Cruikshank, D. P.↗

The Transiting Exocomets in the HD 172555 System

The Earth is thought to have formed dry, in a part of the Solar Nebula deficient in organic material, and to have acquired its organics and water through bombardment by minor bodies. Observations of this process in well-dated systems can provide insight into the probable origin and composition of the bombarding parent bodies. Transiting cometary activity has previously been reported in Ca II for the late-A member of the 241 Myr old Pictoris Moving Group member, HD 172555(Kiefer et al. 2014). We present HST STIS and COS spectra of HD 172555 demonstrating that the star has chromospheric emission and variable in falling gas features in transitions of silicon and carbon ions at times when no Fe II absorption is seen in the UV data, and no Ca II absorption is seen in contemporary optical spectra. The lack of CO absorption and stable gas absorption at the system velocity is consistent with the absence of a cold Kuiper belt analog (Riviere-Marichalar et al. 2012) in this system. The presence of infall in some species at one epoch and others at different epochs suggests that, like Pictoris, there may be more than one family of exocomets. If perturbed into star-grazing orbits by the same mechanism as for Pic, these data suggest that the wide planet frequency among A-early F stars in the PMG is at least 37.5, well above the frequency estimated for young moving groups independent of host star spectral type.

Pictoris Moving Group↗

The Sariçiçek Howardite Fall in Turkey: Source Crater of HED Meteorites on Vesta and Impact Risk of Vestoids

The Sariçiçek howardite meteorite shower consisting of 343 documented stones occurred on September 2, 2015 in Turkey and is the first documented howardite fall. Cosmogenic isotopes show that Sariçiçek experienced a complex cosmic‐ray exposure history, exposed during ~12–14 Ma in a regolith near the surface of a parent asteroid, and that an ~1 m sized meteoroid was launched by an impact 22 ± 2 Ma ago to Earth (as did one‐third of all HED meteorites). SIMS dating of zircon and baddeleyite yielded 4550.4 ± 2.5 Ma and 4553 ± 8.8 Ma crystallization ages for the basaltic magma clasts. The apatite U‐Pb age of 4525 ± 17 Ma, K‐Ar age of ~3.9 Ga, and the U,Th‐He ages of 1.8 ± 0.7 and 2.6 ± 0.3 Ga are interpreted to represent thermal metamorphic and impact‐related resetting ages, respectively. Petrographic; geochemical; and O‐, Cr‐, and Ti‐isotopic studies confirm that Sariçiçek belongs to the normal clan of HED meteorites. Petrographic observations and analysis of organic material indicate a small portion of carbonaceous chondrite material in the Sariçiçek regolith and organic contamination of the meteorite after a few days on soil. Video observations of the fall show an atmospheric entry at 17.3 ± 0.8 km/s from NW; fragmentations at 37, 33, 31, and 27 km altitude; and provide a pre‐atmospheric orbit that is the first dynamical link between the normal HED meteorite clan and the inner Main Belt. Spectral data indicate the similarity of Sariçiçek with the Vesta asteroid family (V‐class) spectra, a group of asteroids stretching to delivery resonances, which includes (4) Vesta. Dynamical modeling of meteoroid delivery to Earth shows that the complete disruption of a ~1 km sized Vesta family asteroid or a ~10 km sized impact crater on Vesta is required to provide sufficient meteoroids ≤4 m in size to account for the influx of meteorites from this HED clan. The 16.7 km diameter Antionia impact crater on Vesta was formed on terrain of the same age as given by the 4He retention age of Sariçiçek. Lunar scaling for crater production to crater counts of its ejecta blanketshow it was formed ~22 Ma ago.

Unsalan, Ozan↗

Physics-Guided Continual Learning for Predicting Emerging Aqueous Organic Redox Flow Battery Material Performance

Aqueous organic redox flow batteries (AORFBs) have gained popularity in renewable energy storage due to their low cost, environmental friendliness and scalability. The rapid discovery of aqueous soluble organic (ASO) redox-active materials necessitates efficient machine learning surrogates for predicting battery performance. The physics-guided continual learning (PGCL) method proposed in this study can incrementally learn data from new ASO electrolytes while addressing catastrophic forgetting issues in conventional machine learning. Using a AORFB database with a thousand potential materials generated by a 780 $\text{cm}^2$ interdigitated cell model, PGCL incorporates AORFB physics to optimize the continual learning task formation and training strategies to retain previously learned battery material knowledge. Finally, the trained PGCL demonstrates its capability in assessing emerging ASO materials within the established parameter space when evaluated with the dihydroxyphenazine isomers.

25 ENERGY STORAGE↗

Organic nonlinear optical materials

Recently, it became clear that organic compounds with delocalized pi electrons show a great nonlinear optical response. Especially, secondary nonlinear optical constants of more than 2 digits were often seen in the molecular level compared to the existing inorganic crystals such as LiNbO3. The crystallization was continuously tried. Organic nonlinear optical crystals have a new future as materials for use in the applied physics such as photomodulation, optical frequency transformation, opto-bistabilization, and phase conjugation optics. Organic nonlinear optical materials, e.g., urea, O2NC6H4NH2, I, II, are reviewed with 50 references.

Umegaki, S.↗

Singlet fission

Singlet fission (SF) is a process whereby a photo-excited singlet exciton spontaneously splits into lower energy triplet excitons. This process has been known to occur in select organic materials for over 50 years but in the past was viewed as a curiosity and not as a problem worthy of focused attention. Over the past decade, this viewpoint has changed as the promising use of SF to improve photovoltaic efficiency has spurred vast activity, which has revealed the richness of the phenomenon. Currently, our understanding of the role played by various bright and dark states and their couplings to vibrations and to each other and by chemical composition and packing, among other factors, has enabled a large increase in the number of viable SF systems as well as a far deeper understanding of the process itself. These advances have allowed for the demonstration of proof-of-concept increases in the solar cell efficiency via the use of SF materials in simple tandem cells and as sensitizers in conjunction with conventional photovoltaics. Indeed, concepts surrounding the field have now invaded other fields, with a prominent example being the use of photon upconversion associated with triplet–triplet fusion (the inverse process to SF) in organic chemistry and photocatalysis. The 23 research articles in this special topic showcase recent cutting-edge advances in the field and highlight the diverse new directions being explored in the field of SF.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low-dimensional metal–organic frameworks: a pathway to design, explore and tune magnetic structures

Here, the magnetic structure adopted by a material relies on symmetry, the hierarchy of exchange interactions between magnetic ions and local anisotropy. A direct pathway to control the magnetic interactions is to enforce dimensionality within the material, from zero-dimensional isolated magnetic ions, one-dimensional (1D) spin-chains, two-dimensional (2D) layers to three-dimensional (3D) order. Being able to design a material with a specific dimensionality for the phenomena of interest is non-trivial. While many advances have been made in the area of inorganic magnetic materials, organic compounds offer distinct and potentially more fertile ground for material design. In particular magnetic metal–organic frameworks (mMOFs) combine magnetism with non-magnetic property functionality on the organic linkers within the structural framework, which can further be tuned with mild perturbations of pressure and field to induce phase transitions. Here, it is examined how neutron scattering measurements on mMOFs can be used to directly determine the magnetic structure when the magnetic ions are in a 2D layered environment within the wider 3D crystalline framework. The hydrated formate, in deuterated form, Co(DCOO) 2 ·2D 2 O, which was one of the first magnetic MOFs to be investigated with neutron diffraction, is reinvestigated as an exemplar case.

magnetism↗

Teaching Soil Science in Primary and Secondary Schools

Earth's thin layer of soil is a fragile resource, made up of minerals, organic materials, air, water, and billions of living organisms. Soils plays a variety of critical roles that sustain life on Earth. If we think about soil, we tend to see it first as the source of most of the food we eat and the fibers we use, such as wood and cotton. Few students realize that soils also provide the key ingredients to many of the medicines (including antibiotics), cosmetics, and dyes that we use. Fewer still understand the importance of soils in integrating, controlling, and regulating the movement of air, water, materials, and energy between the hydrosphere, lithosphere, atmosphere, and biosphere. Because soil sustains life, it offers both a context and a natural laboratory for investigating these interactions. The enclosed poster, which integrates soil profiles with typical landscapes in which soils form, can also help students explore the interrelationships of Earth systems and gain an understanding of our soil resources. The poster, produced jointly by the American Geological Institute and the Soil Science Society of America, aims to increase awareness of the importance of soil, as does the GLOBE (Global Learning and Observations To Benefit the Environment) Program. Vice President Al Gore instituted the GLOBE Program on Earth Day of 1993 to increase environmental awareness of individuals throughout the world, contribute to a better scientific understanding of the Earth, and help all students reach higher levels of achievement in science and mathematics. GLOBE functions as a partnership between scientists, students, and teachers in which scientists design protocols for specific measurements they need for their research that can be performed by K-12 students. Teachers are trained in the GLOBE protocols and teach them to their students. Students make the measurements, enter data via the Internet to a central data archive, and the data becomes available to scientists and the general community. Students benefit by having a "hands-on"experience in science, math, and technology, using their local environment as a learning laboratory, as well as contact with scientists and other students around the world. Soil investigations have become an essential component of GLOBE. The protocols that have been developed so far within the GLOBE program include GPS Location, Atmosphere/Climate, Soil Characterization, Soil Moisture and Temperature, Land Cover/Biometry, Hydrology, and Satellite Image Classification. For the GLOBE Soil Characterization Protocol, students explore the physical. chemical, and morphological properties of the soil at their study site. They are asked to dig a pit or use an auger to about 1 meter at at least 2 sites.

Levine, Elissa R.↗

Impact of Mount St. Helens eruption on hydrology and water quality

The 1980 eruptions of Mount St. Helens in southeast Washington resulted in a pronounced effect on the surface and ground water resources of the state. In response to the volcanic activity, the U.S. Geological Survey intensified statewide surface and ground water sampling programs to determine the nature and magnitude of the volcanic-induced variations. Streams to the east of Mount St. Helens received the major ash fallout. Chemical effects were best noted in smaller streams sampled 60 to 70 miles northeast of Mount St. Helens. The chemical variations observed were pronounced but short lived. Sulfate and chloride increases in anionic composition were prevalent immediately following the eruption; however, the original bicarbonate predominance was again attained within several days. Suspended iron and aluminum concentrations were similarly elevated during the period of greatest ash deposition (highest turbidity); however, the dissolved concentrations remained relatively constant. Depressions of pH were minor and short lived. Streams draining to the south, tributaries to the Columbia river, showed little observable changes in water chemistry. Streams draining to the west (Toutle river and its tributaries) were compositionally affected by the various volcanic activities. Chloride and sulfate anion percentage exceeded the bicarbonate percentage up to one month following the eruption period. Streams and lakes sampled in the immediate vicinity of Mount St. Helens, in addition to trace metals, contained organic compounds derived from decomposing wood buried in the debris deposits. This organic material may constitute a significant source of organic compounds to surface and ground water for some time to come.

Bonelli, J. E.↗

Biomass-burning emissions and associated haze layers over Amazonia

The characteristics of haze layers, which were visually observed over the central Amazon Basin during many of the Amazon Boundary Layer Experiment 2A flights in July/August 1985, were investigated by remote and in situ measurements, using the broad range of instrumentation and sampling equipment on board the Electra aircraft. It was found that these layers strongly influenced the chemical and optical characteristics of the atmosphere over the eastern Amazon Basin. Relative to the regional background, the concentrations of CO, CO2, O3, and NO were significantly elevated in the plumes and haze layers, with the NO/CO ratio in fresh plumes much higher than in the aged haze layers. The haze aerosol was composed predominantly of organic material, NH4, K(+), NO3(-), SO4(2-), and organic anions (formate, acetate, and oxalate).

Andreae, M. O.↗

A semianalytic radiance model of ocean color

A semianalytical radiance model is developed which predicts the upwelled spectral radiance at the sea surface as a function of the phytoplankton pigment concentration for Morel Case 1 waters. The model is in good agreement with experimental measurements carried out in waters which were not included in the data base used to derive it. It suggests that the observed variability in the radiance is due to variations in the backscattering of plankton and the associated detrital material. The model is extended to include other material in the water, such as dissolved organic material, referred to as yellow substances, and detached coccoliths from coccolithophorids, e.g., Emiliana huxleyi. Potential applications include an improved biooptical algorithm for the retrieval of pigment concentrations from satellite imagery in the presence of interference from detached coccoliths and an improved atmospheric correction for satellite imagery. The model also serves to identify and to interpret deviations from Case 1 waters.

Gordon, Howard R.↗