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The impact of different neutrino transport methods on multidimensional core-collapse supernova simulations
Neutrinos play a crucial role in the core-collapse supernova (CCSN) explosion mechanism. The requirement of accurately calculating the transport of neutrinos makes simulations of the CCSN mechanism extremely challenging and computationally expensive. Historically, this stiff challenge has been met by making approximations to the full transport equation. In this work, we compare CCSN simulations in one- and two-dimensions with three approximate neutrino transport schemes, each implemented in the FLASH simulation framework. We compare a two-moment M1 scheme with an analytic closure (M1), the isotropic diffusion source approximation (IDSA), and the advanced spectral leakage method. We identify and discuss the advantages and disadvantages of each scheme. For each approximate transport scheme, we use identical grid setups, hydrodynamics, and gravity solvers to investigate the transport effects on supernova shock dynamics and neutrino quantities. We find that the transport scheme has a small effect on the evolution of protoneutron star (PNS) radius, PNS mass, and the mass accretion rate. The neutrino luminosities, mean energies, and shock radii have a ~10%–20% quantitative difference but the overall qualitative trends are fairly consistent between all three approximations. We find larger differences in the gain region properties, including the gain region mass and the net heating rate in the gain region, as well as the strength of PNS convection in the core. We investigate the progenitor, nuclear equation of state, and stochastic perturbation dependence of our simulations and find similar magnitudes of impact on key quantities. We also compare the computational expense of the various approximations.
Iron X-ray Transmission at Temperature Near 150 eV Using the National Ignition Facility: First Measurements and Paths to Uncertainty Reduction
Discrepancies exist between theoretical and experimental opacity data for iron, at temperatures 180–195 eV and electron densities near 3 × 1022/cm3, relevant to the solar radiative-convective boundary. Another discrepancy, between theory and helioseismic measurements of the boundary’s location, would be ameliorated if the experimental opacity is correct. To address these issues, this paper details the first results from new experiments under development at the National Ignition Facility (NIF), using a different method to replicate the prior experimental conditions. In the NIF experiments, 64 laser beams indirectly heat a plastic-tamped rectangular iron-magnesium sample inside a gold cavity. Another 64 beams implode a spherical plastic shell to produce a continuum X-ray flash which backlights the hot sample. An X-ray spectrometer records the transmitted X-rays, the unattenuated X-rays passing around the sample, and the sample’s self-emission. From these data, X-ray transmission spectra are inferred, showing Mg K-shell and Fe L-shell X-ray transitions from plasma at a temperature of ~150 eV and electron density of ~8 × 1021/cm3. These conditions are similar to prior Z measurements which agree better with theory. The NIF transmission data show statistical uncertainties of 2–10%, but various systematic uncertainties must be addressed before pursuing quantitative comparisons. The paths to reduction of the largest uncertainties are discussed. Once the uncertainty is reduced, future NIF experiments will probe higher temperatures (170–200 eV) to address the ongoing disagreement between theory and Z data.
Influence on anaerobic digestion by intermediate thermal hydrolysis of waste activated sludge and co-digested wheat straw
Highlights: • Intermediate thermal hydrolysis mediates further energy recovery. • Straw for co-digestion boosts methane production. • Thermal hydrolysis increases VFA concentration but lowers pH. • Thermal hydrolysis without flash has optimum at 170 °C and 30 min. - Abstract: This paper analyses time (30 and 60 min) and temperature (120–190 °C) effects of intermediate thermal hydrolysis (ITHP) in a two-step anaerobic digestion of waste activated sludge (WAS) with and without wheat straw as a co-substrate. Effects were analyzed by measuring biochemical methane potential for 60 days and assessing associated kinetic and chemical data. Compared to non-treatment, ITHP increased the secondary step methane yield from 52 to 222 L CH{sub 4} kg VS{sup −1} and from 147 to 224 L CH{sub 4} kg VS{sup −1} for pre-digested WAS and pre-co-digested WAS respectively at an optimum of 170 °C and 30 min. The hydrolysis coefficients (k{sub hyd}) increased by up to 127% following treatment. Increasing ITHP time from 30 to 60 min showed ambiguous results regarding methane yields, whilst temperature had a clear and proportional effect on the concentrations of acetic acid. The energy balances were found to be poor and dewatering to increase total solids above the values tested here is necessary for this process to be energetically feasible.
Mechanistic studies of hydrogen evolution in aqueous solution catalyzed by a tertpyridine-amine cobalt complex
The ability of cobalt-based transition metal complexes to catalyze electrochemical proton reduction to produce molecular hydrogen has resulted in a large number of mechanistic studies involving various cobalt complexes. In addition, while the basic mechanism of proton reduction promoted by cobalt species is well understood, the reactivity of certain reaction intermediates, such as Co I and Co III –H, is still relatively unknown owing to their transient nature, especially in aqueous media. In this work we investigate the properties of intermediates produced during catalytic proton reduction in aqueous solutions promoted by the [(DPA-Bpy)Co(OH₂)] n+ (DPA-Bpy = N,N -bis(2-pyridinylmethyl)-2,20-bipyridine-6-methanamine) complex ([Co(L)(OH₂)] n+ where L is the pentadentate DPA-Bpy ligand or [ Co (OH₂)] n+ as a shorthand). Experimental results based on transient pulse radiolysis and laser flash photolysis methods, together with electrochemical studies and supported by DFT calculations indicate that, while the water ligand is strongly coordinated to the metal center in the oxidation state 3+, one-electron reduction of the complex to form a Co II species results in weakening the Co–O bond. The further reduction to a Co I species leads to the loss of the aqua ligand and the formation of [ Co I –VS)]⁺ (VS = vacant site). Interestingly, DFT calculations also predict the existence of a [Co I (κ⁴-L)(OH₂)]⁺ species at least transiently, and its formation is consistent with the experimental Pourbaix diagram. Both electrochemical and kinetics results indicate that the Co I species must undergo some structural change prior to accepting the proton, and this transformation represents the rate-determining step (RDS) in the overall formation of [ Co III –H]⁺. We propose that this RDS may originate from the slow removal of a solvent ligand in the intermediate [Co I (κ⁴-L)(OH₂)]⁺ in addition to the significant structural reorganization of the metal complex and surrounding solvent resulting in a high free energy of activation.
Comparison of crystal growth and thermoelectric properties of n-type Bi-Se-Te and p-type Bi-Sb-Te nanocrystalline thin films: Effects of homogeneous irradiation with an electron beam
The effects of homogenous electron beam (EB) irradiation on the crystal growth and thermoelectric properties of n-type Bi-Se-Te and p-type Bi-Sb-Te thin films were investigated. Both types of thin films were prepared by flash evaporation, after which homogeneous EB irradiation was performed at an acceleration voltage of 0.17 MeV. For the n-type thin films, nanodots with a diameter of less than 10 nm were observed on the surface of rice-like nanostructures, and crystallization and crystal orientation were improved by EB irradiation. The resulting enhancement of mobility led to increased electrical conductivity and thermoelectric power factor for the n-type thin films. In contrast, the crystallization and crystal orientation of the p-type thin films were not influenced by EB irradiation. The carrier concentration increased and mobility decreased with increased EB irradiation dose, possibly because of the generation of defects. As a result, the thermoelectric power factor of p-type thin films was not improved by EB irradiation. The different crystallization behavior of the n-type and p-type thin films is attributed to atomic rearrangement during EB irradiation. Selenium in the n-type thin films is more likely to undergo atomic rearrangement than the other atoms present, so only the crystallinity of the n-type Bi-Se-Te thin films was enhanced.
Enhanced thermoelectric properties of phase-separating bismuth selenium telluride thin films via a two-step method
A two-step method that combines homogeneous electron beam (EB) irradiation and thermal annealing has been developed to enhance the thermoelectric properties of nanocrystalline bismuth selenium telluride thin films. The thin films, prepared using a flash evaporation method, were treated with EB irradiation in a N{sub 2} atmosphere at room temperature and an acceleration voltage of 0.17 MeV. Thermal annealing was performed under Ar/H{sub 2} (5%) at 300 °C for 60 min. X-ray diffraction was used to determine that compositional phase separation between bismuth telluride and bismuth selenium telluride developed in the thin films exposed to higher EB doses and thermal annealing. We propose that the phase separation was induced by fluctuations in the distribution of selenium atoms after EB irradiation, followed by the migration of selenium atoms to more stable sites during thermal annealing. As a result, thin film crystallinity improved and mobility was significantly enhanced. This indicates that the phase separation resulting from the two-step method enhanced, rather than disturbed, the electron transport. Both the electrical conductivity and the Seebeck coefficient were improved following the two-step method. Consequently, the power factor of thin films that underwent the two-step method was enhanced to 20 times (from 0.96 to 21.0 μW/(cm K{sup 2}) that of the thin films treated with EB irradiation alone.
Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO) 5 , Fe(CO) 4 , and Fe(CO) 3
The prototypical photoinduced dissociation of Fe(CO) 5 in the gas phase is used to test time-resolved x-ray photoelectron spectroscopy for studying photochemical reactions. Upon one-photon excitation at 266 nm, Fe(CO) 5 successively dissociates to Fe(CO) 4 and Fe(CO) 3 along a pathway where both fragments retain the singlet multiplicity of Fe(CO) 5 . The x-ray free-electron laser FLASH is used to probe the reaction intermediates Fe(CO) 4 and Fe(CO) 3 with time-resolved valence and core-level photoelectron spectroscopy, and experimental results are interpreted with ab initio quantum chemical calculations. Changes in the valence photoelectron spectra are shown to reflect changes in the valence-orbital interactions upon Fe–CO dissociation, thereby validating fundamental theoretical concepts in Fe–CO bonding. Chemical shifts of CO 3σ inner-valence and Fe 3p core-level binding energies are shown to correlate with changes in the coordination number of the Fe center. We interpret this with coordination-dependent charge localization and core-hole screening based on calculated changes in electron densities upon core-hole creation in the final ionic states. This extends the established capabilities of steady-state electron spectroscopy for chemical analysis to time-resolved investigations. Lastly, it could also serve as a benchmark for how charge and spin density changes in molecular dissociation and excited-state dynamics are expressed in valence and core-level photoelectron spectroscopy.
Condor : a simulation tool for flash X-ray imaging
Flash X-ray imaging has the potential to determine structures down to molecular resolution without the need for crystallization. The ability to accurately predict the diffraction signal and to identify the optimal experimental configuration within the limits of the instrument is important for successful data collection. This article introduces Condor , an open-source simulation tool to predict X-ray far-field scattering amplitudes of isolated particles for customized experimental designs and samples, which the user defines by an atomic or a refractive index model. The software enables researchers to test whether their envisaged imaging experiment is feasible, and to optimize critical parameters for reaching the best possible result. It also aims to support researchers who intend to create or advance reconstruction algorithms by simulating realistic test data. Condor is designed to be easy to use and can be either installed as a Python package or used from its web interface (http://lmb.icm.uu.se/condor). X-ray free-electron lasers have high running costs and beam time at these facilities is precious. Data quality can be substantially improved by using simulations to guide the experimental design and simplify data analysis.
Accelerated thermal property mapping of TRISO advanced nuclear fuel
TRistructural ISOtropic (TRISO) fuel is a leading-edge nuclear fuel form representing a departure from the more traditional nuclear fuel forms utilized in the reactor fleet of today. Rather than a monolithic fuel pellet of uranium dioxide, integral fuel forms containing TRISO fuel are composed of thousands of microencapsulated uranium-bearing fuel kernels and individually coated with multiple layers of pyrolytic carbon and silicon carbide. These multilayered ceramic coatings serve as an environmental barrier to ensure radioactive and chemically reactive fission products are contained within the reactor fuel elements, but also participate in the transfer of heat generated in the nuclear fuel to the coolant – the primary purpose of a nuclear reactor. Since traditional thermal property measurement techniques, such as laser flash analysis, would be unable to resolve the thermal properties of the individual TRISO coating layers, a simplified frequency-domain thermoreflectance technique has been developed to rapidly map the thermal properties of TRISO particles. Using this technique, the thermal properties of TRISO particles have been mapped from room temperature up to 1000 °C to examine the spatial variation and temperature-dependency of the thermal properties within each layer. Additionally, spatial-domain thermoreflectance was used to examine the anisotropy of the thermal properties for each layer at different locations within a single TRISO particle, and across multiple TRISO particles to assess the intra- and inter-particle uniformity of thermal properties, respectively. To elucidate the underlying causes for the measured variations in thermal properties, scanning electron microscopy and Raman spectroscopy were used to examine variations in microstructure and chemical bonding within the different coating layers. Results from this work are then compared with previous examinations of TRISO fuel particles and microstructurally driven mechanisms for the variations in the measured thermal properties of the different carbonaceous layers are discussed.
Numerical demonstration of Biermann-generated magnetic fields in a laser-driven cylindrical implosion platform
We present two-dimensional radiation-magnetohydrodynamics FLASH simulations studying Biermann battery generated magnetic fields in a convergent geometry based on modifying an existing laser direct drive cylindrical implosion platform at Los Alamos National Laboratory. During the laser driven implosion, instabilities can arise as the target converges, and in a plasma, such instabilities can generate magnetic fields via the Biermann battery. After significant redesign (lowering the inner foam fill density, deceasing the ablator mass, and modifying the laser pulse), we demonstrate that magnetic fields reach strengths of many hundred kilogauss and persist over a nanosecond time scale. Such results pave the way for an experimental campaign for further code verification and validation.
Metallic Nanocomposites as Next-Generation Thermal Interface Materials
Thermal interface materials (TIMs) are an integral and important part of thermal management in electronic devices. The electronic devices are becoming more compact and powerful. This increase in power processed or passing through the devices leads to higher heat fluxes and makes it a challenge to maintain temperatures at the optimal level during operation. Herein, we report a free standing nanocomposite TIM in which boron nitride nanosheets (BNNS) are uniformly dispersed in copper matrices via an organic linker, thiosemicarbazide. Integration of these metal-organic-inorganic nanocomposites was made possible by a novel electrodeposition technique where the functionalized BNNS (f-BNNS) experience the Brownian motion and reach the cathode through diffusion, while the nucleation and growth of the copper on the cathode occurs via the electrochemical reduction. Once the f-BNNS bearing carbonothioyl/thiol groups on the terminal edges come into the contact with copper crystals, the chemisorption reaction takes place. We performed thermal, mechanical, and structural characterization of these nanocomposites using scanning electron microcopy (SEM), diffusive laser flash (DLF) analysis, phase-sensitive transient thermoreflectence (PSTTR), and nanoindentation. The nanocomposites exhibited a thermal conductivity ranging from 211 W/mK to 277 W/mK at a filler mass loading of 0-12 wt.percent. The nanocomposites also have about 4 times lower hardness as compared to copper, with values ranging from 0.27 GPa to 0.41 GPa. The structural characterization studies showed that most of the BNNS are localized at grain boundaries - which enable efficient thermal transport while making the material soft. PSTTR measurements revealed that the synergistic combinations of these properties yielded contact resistances on the order of 0.10 to 0.13 mm2K/W, and the total thermal resistance of 0.38 to 0.56 mm2K/W at bondline thicknesses of 30-50 um. The coefficient of thermal expansion (CTE) of the nanocomposite is 11 ppm/K, which lies between the CTEs of aluminum (22 ppm/K) and silicon (3 ppm/K), which are common heat sink and heat source materials, respectively. The nanocomposite can also be deposited directly on to heat sink which will simplify the packaging processes by removing one possible element to assemble. These unique properties and ease of assembly makes the nanocomposite a promising next-generation TIM.
Metallic Nanocomposites as Next-Generation Thermal Interface Materials: Preprint
Thermal interface materials (TIMs) are an integral and important part of thermal management in electronic devices. The electronic devices are becoming more compact and powerful. This increase in power processed or passing through the devices leads to higher heat fluxes and makes it a challenge to maintain temperatures at the optimal level during operation. Herein, we report a free standing nanocomposite TIM in which boron nitride nanosheets (BNNS) are uniformly dispersed in copper matrices via an organic linker, thiosemicarbazide. Integration of these metal-organic-inorganic nanocomposites was made possible by a novel electrodeposition technique where the functionalized BNNS (f-BNNS) experience the Brownian motion and reach the cathode through diffusion, while the nucleation and growth of the copper on the cathode occurs via the electrochemical reduction. Once the f-BNNS bearing carbonothioyl/thiol groups on the terminal edges come into the contact with copper crystals, the chemisorption reaction takes place. We performed thermal, mechanical, and structural characterization of these nanocomposites using scanning electron microcopy (SEM), diffusive laser flash (DLF) analysis, phase-sensitive transient thermoreflectence (PSTTR), and nanoindentation. The nanocomposites exhibited a thermal conductivity ranging from 211 W/mK to 277 W/mK at a filler mass loading of 0-12 wt.percent. The nanocomposites also have about 4 times lower hardness as compared to copper, with values ranging from 0.27 GPa to 0.41 GPa. The structural characterization studies showed that most of the BNNS are localized at grain boundaries - which enable efficient thermal transport while making the material soft. PSTTR measurements revealed that the synergistic combinations of these properties yielded contact resistances on the order of 0.10 to 0.13 mm2K/W, and the total thermal resistance of 0.38 to 0.56 mm2K/W at bondline thicknesses of 30-50 um. The coefficient of thermal expansion (CTE) of the nanocomposite is 11 ppm/K, which lies between the CTEs of aluminum (22 ppm/K) and silicon (3 ppm/K), which are common heat sink and heat source materials, respectively. The nanocomposite can also be deposited directly on to heat sink which will simplify the packaging processes by removing one possible element to assemble. These unique properties and ease of assembly makes the nanocomposite a promising next-generation TIM.
The HyMeX Special Observation Period in Central Italy: Precipitation Measurements, Retrieval Techniques and Preliminary Results
The Mediterranean area concentrates the major natural risks related to the water cycle, including heavy precipitation and flash-flooding during the fall season. The capability to predict such high-impact events remains weak because of the contribution of very fine-scale processes and their non-linear interactions with the larger scale processes. These societal and science issues motivate the HyMeX (Hydrological cycle in the Mediterranean Experiment, http://www.hymex.orgl) experimental programme. HyMeX aims at a better quantification and understanding of the water cycle in the Mediterranean with emphasis on intense events. The observation strategy of HyMEX is organized in a long-term (4 years) Enhanced Observation Periods (EOP) and short-term (2 months) Special Observation Periods (SOP). HyMEX has identified 3 main Mediterranean target areas: North-West (NW), Adriatic (A) and South-East (SE). Within each target area several hydrometeorological sites for heavy rainfall and flash flooding have been set up. The hydrometeorological sire in Central Italy (CI) is interested by both western and eastern fronts coming from the Atlantic Ocean and Siberia, respectively. Orographic precipitations play an important role due to the central Apennine range, which reaches nearly 3000 m (Gran Sasso peak). Moreover, convective systems commonly develop in CI during late summer and beginning of autumn, often causing localized hailstorms with cluster organized cells. Western fronts may heavily hit the Tiber basin crossing large urban areas (Rome), whereas eastern fronts can cause flash floods along the Adriatic coastline. Two major basins are involved within Cl region: Tiber basin (1000 km long) and its tributary Aniene and the Aterno-Pescara basin (300 km long). The first HyMeX SOP1.1 was carried out from Sept. till Nov. 2012 in the NW target area The Italian SOP1.1 was coordinated by the Centre of Excellence CETEMPS, University of L'Aquila, a city located in the CI heart. The CI area was covered by a uniquely dense meteorological instrumentation thanks to a synergy between Italian institutions and NASA-GSFC. The following RADARs were operated: a Doppler single-polarization C-band radar located at Mt Midia; the Polar 55C Doppler dual-polarization C-band radar located in Rome; a Doppler C-hand polarimetric radar located at Il Monte (Abnazo); a polarimetric X-band mini-radar in L' Aquila; a polarimetric X-hand portable mini-radar in Rome; a single-polarization X-band mini-radar in Rome. DISDROMETERs were also deployed: 4 Parsivel optical disdrometers in Rome (at Sapienza, CNR-ISAC and CNR-INSEAN); 1 2D-video disdrometer in Rome; 3 Parsivels optical disdrometer respectively in L'Aquila (Abnazo), Avezzano (Abruzzo) and Pescara (Abnazo). Other INSTRUMENTS were available: 1 K-band vertically-pointing micro rain-radar (MRR), 2 Pludix X-band disdrometers, 1 VLF lightning sensor, 1 microwave radiometer at 23-31 GHz in Rome (at Sapienza); the raingauge network with more than 200 stations in Central Italy. Three overpasses in CI were also performed by the Falcon 20 aircraft equipped with the 950Hz cloud radar RASTA Analysis of the SOP1.1 main events in CI will be described by focusing on the raindrop size distribution statistics and its geographical variability. Intercomparison of rainfall estimates from disdrometers, raingauges and radars will be illustrated with the aim to provide a quality-controlled and physically consistent rainfall dataset for meteorological modeling validation and assimilation purposes.
Spray Foam Exterior Insulation with Stand-Off Furring - New York
IBACOS and Green Homes America 1 (GHA) collaborated with the New York State Energy Research and Development Authority (NYSERDA) Advanced Buildings Program to research a variation of a commercial curtain wall assembly for residential construction as part of a comprehensive whole-house deep energy retrofit (DER) package. The advantages of this strategy include minimizing the physical connections to each individual existing wall stud, using closedcell spray foam to encapsulate existing siding materials including lead paint, and creating a vented rain screen assembly to promote drying. As Moore (2011) states, "Closed-cell foam acts as air-sealing, insulation, and secondary drainage plane..." Field installations on a limited number of houses indicate that the incremental cost when installed as part of a typical siding and window replacement job adds approximately $10/ft2 of wall area. 2 x 4 framing members were attached to the wall at band joists and top plates using "L" clips, and spray foam was used to insulate the wall after the framing was installed. Windows were installed as the framing was put up, including extension jambs. Key lessons learned include the following: (1) The installed cost of the spray foam system was comparable to the installed cost of the rigid foam and furring strips. (2) Spray foam should be applied in such a way that it locks the framing members in place before the remaining foam is installed in the field of the wall. The spray foam has a tendency to move the new wall framing as it expands. Best practice is to "picture frame" the wall framing with spray foam and then apply the spray foam in the field of each bay. (3) Variations in the existing siding conditions must be accounted for when attaching the ledger boards and wall framing. A best practice is to uniformly shim the ledger boards off the walls so the new framing is a uniform distance from the ledger boards and the inside surface of the interior framing. This is important primarily for window and door installation and the associated extension jambs and trim. (4) From a sequencing perspective, it is advantageous to replace the windows at the same time as the exterior walls are being built. This requires a crew that can perform a number of different tasks (e.g., framing, flashing, window install, trim carpentry) and does not lend itself to subcontracting this approach piecemeal (e.g., framing subcontractor, window installer, drainage plane installer, trim carpenter). (5) Application of the brackets and associated fastener screws was more time consuming than anticipated. (6) It is important for the spray foam contractor to perform all preparatory work, which in this case included placing plastic over the windows and exposed foundation to minimize or eliminate the possibility of damage due to overspray.
Attractive Improvement in Structural, Magnetic, Optical, and Antimicrobial Activity of Silver Delafossite by Fe/Cr Doping
This paper presented a novel method of AgX O{sub 2} (X = Fe or Cr) delafossite using flash auto-combustion technique. X-ray diffraction pattern (XRD) clarified single-phase structure. The morphology was analyzed by high-resolution transmission electron microscopy (HRTEM) and field emission scanning electron microscopy (FESEM). The composition of the samples was determined using energy dispersive X-ray (EDX) analysis. The particle size estimated from HRTEM, FESEM, and XRD analyses revealed that the samples were in the nanoscale range. The magnetic hysteresis loop of the samples was measured at room temperature (300 K) and at low temperatures (200 and 100 K). Rare behavior by shifting the hysteresis loop horizontally was observed for AgCrO{sub 2} delafossite at low temperatures (200 and 100 K). The optical properties were measured for the investigated samples. The antimicrobial study promoted that AgFeO{sub 2} delafossite had a strong antibacterial activity against Gram-positive and Gram-negative bacteria than that of AgCrO{sub 2} delafossite. However, no activity appeared for both samples against fungus micro-organisms. As a result, AgFeO{sub 2} delafossite could be applied in cancer diagnoses, biomedical applications, and energy storage in solar cell. Moreover, AgCrO{sub 2} delafossite could be applied as a photocathode in a dye-sensitized solar cell and biomedical applications.
Correlated solvent coordinates accelerate multi-donor proton-coupled electron transfer
The rate of charge transfer within a discrete donor–acceptor (D/A) pair is well-described by semi-classical electron transfer theory, but the effects of multiple equivalent redox sites remain less understood. We report a series of ground-state intramolecular proton-coupled electron transfer (PCET) complexes designed to isolate the effects of donor number, N, while holding geometry, coupling, and driving forces constant. The [Ru(L) 3−N (OH) N ] 2+ complexes incorporate one, two, or three identical phenolic electron donors linked to Ru through rigid phenanthroline bridges (OH = 2,4-di-tert-butyl-6-(1-methyl-1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol). Upon flash photolysis and oxidative quenching with methyl viologen (MV 2+ ), the transient Ru(III) oxidizes an appended phenol by PCET with the hydrogen-bonded imidazole nitrogen atom functioning as the base. The rate increased by 3.4-fold and 5.7-fold (1.7-fold and 1.9-fold after statistical correction) for two- and three-donor complexes compared to the single-donor system. The supra-statistical acceleration is attributed to a reduced effective outer sphere reorganization energy (λ m ) modeled by a partially shared solvent reaction coordinate, in which a subset of solvent dipoles is already oriented to stabilize charge from any donor. The final phenoxyl radical state is localized due to the transfer of a proton, and the recombination reaction with the viologen radical is not accelerated. These results demonstrate the effects of solvent dynamics on intramolecular PCET rates, offering a new strategy for the design of synthetic charge transfer systems.
Memristive behavior in a junctionless flash memory cell
We report charge storage based memristive operation of a junctionless thin film flash memory cell when it is operated as a two terminal device by grounding the gate. Unlike memristors based on nanoionics, the presented device mode, which we refer to as the flashristor mode, potentially allows greater control over the memristive properties, allowing rational design. The mode is demonstrated using a depletion type n-channel ZnO transistor grown by atomic layer deposition (ALD), with HfO{sub 2} as the tunnel dielectric, Al{sub 2}O{sub 3} as the control dielectric, and non-stoichiometric silicon nitride as the charge storage layer. The device exhibits the pinched hysteresis of a memristor and in the unoptimized device, R{sub off}/R{sub on} ratios of about 3 are presented with low operating voltages below 5 V. A simplified model predicts R{sub off}/R{sub on} ratios can be improved significantly by adjusting the native threshold voltage of the devices. The repeatability of the resistive switching is excellent and devices exhibit 10{sup 6 }s retention time, which can, in principle, be improved by engineering the gate stack and storage layer properties. The flashristor mode can find use in analog information processing applications, such as neuromorphic computing, where well-behaving and highly repeatable memristive properties are desirable.