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Grid generation for general three-dimensional configurations

A suitable grid system for complex three dimensional configurations such as wing/body/nacelle shape for the solution of nonlinear transonic flow problems was constructed. Two approaches were explored based on Thompson's body fitted coordinate concept. The most general approach was to divide the computational domain into multiple rectangular blocks where the configuration itself was also represented by a set of blocks whose structure follows the natural lines of the configuration. The block structured grid system was adaptable to complex configurations and gives good grid quality near physical corners. However, it introduced algorithm issues for the flow solution concerning the treatment of nonanalytic grid block boundaries and nonstandard grid cells. These issues were explored in relation to the grid generation. A more limited approach treats a wing/body configuration with only a single rectangular block in computational space. The issues involving nonstandard cells were avoided, but other limitations on grid resolution appear. Both a linear and a nonlinear system of grid generation equations were developed including methods of grid control.

Lee, K. D.↗

Molecular Level Differences in Ionic Solvation and Transport Behavior in Ethylene Oxide-Based Homopolymer and Block Copolymer Electrolytes

Block copolymer electrolytes (BCE) such as polystyrene-block-poly(ethylene oxide) (SEO) blended with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and composed of mechanically robust insulating and rubbery conducting nanodomains are promising solid-state electrolytes for Li batteries. Here, we compare ionic solvation, association, distribution, and conductivity in SEO-LiTFSI BCEs and their homopolymer PEO-LiTFSI analogs toward a fundamental understanding of the maximum in conductivity and transport mechanisms as a function of salt concentration. Ionic conductivity measurements reveal that SEO-LiTFSI and PEO-LiTFSI exhibit similar behaviors up to a Li/EO ratio of 1/12, where roughly half of the available solvation sites in the system are filled, and conductivity is maximized. As the Li/EO ratios increase to 1/5 the conductivity, of the PEO-LiTFSI drops nearly 3-fold, while the conductivity of SEO-LiTFSI remains constant. FTIR spectroscopy reveals that additional Li cations in the homopolymer electrolyte are complexed by additional EO units when the Li/EO ratio exceeds 1/12, while in the BCE, the proportion of complexed and uncomplexed EO units remains constant; Raman spectroscopy data at the same concentrations show that Li cations in the SEO-LiTFSI samples tend to coordinate more to their counteranions. Atomistic-scale molecular dynamics simulations corroborate these results and further show that associated ions tend to segregate to the SEO-LiTFSI domain interfaces. The opportunity for "excess" salt to be sequestered at BCE interfaces results in the retention of an optimum ratio of uncompleted and complexed PEO solvation sites in the middle of the conductive nanodomains of the BCE and maximized conductivity over a broad range of salt concentrations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Zinc transport in hydrothermal fluids: On the roles of pressure and sulfur vs. chlorine complexing

Here, we provide an experimental confirmation of the suggestion, based on thermodynamic simulations and extrapolations (Zhong et al. 2015), that Zn is transported in the form of chloride complexes in most shallow hydrothermal systems, while bisulfide complexes become increasingly important in deep hydrothermal systems. We used in situ X-ray absorption spectroscopy (XAS) diamond anvil cell experiments to determine Zn(II) speciation in a 1 m NaHS + 0.2 m HCl solution in contact with sphalerite. XANES data clearly show that Zn coordinates to chloride and/or oxygen ligands from room temperature up to and including 200 C, and then at higher temperatures (≥ 300 C) and pressures (> 2 kbar) changes to complexing with sulfur. Our data confirm that bisulfide complexes become increasingly important at high pressure and temperature, due to an increase in sulfur solubility and to favorable entropy contributions for bisulfide versus chloride complexes.

36 MATERIALS SCIENCE↗

A sulphur and uranium fiesta! Synthesis, structure, and characterization of neutral terminal uranium(VI) monosulphide, uranium(VI) η 2 -disulphide, and uranium(IV) phosphine sulphide complexes

Here, three new uranium species (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(=S), (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(η 2 -S 2 ), and (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(S=PMe 3 ) were synthesized and fully characterized by a combination of NMR, IR, and UV/vis–NIR spectroscopies, elemental analysis, and cyclic voltammetry. The solid state structures of (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(=S) and (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(η 2 -S 2 ) were also determined. The compound (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(=S) is the first neutral uranium complex with a terminal sulphido ligand, and (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(S=PMe 3 ) is the first uranium compound with a coordinated phosphine sulphide ligand. The phosphine sulphide adduct, (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(S=PMe 3 ), can be synthesized either by reaction of the uranium(IV) complex (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(thf) with S=PMe 3 or by the reaction of the uranium(VI) terminal sulphido complex (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(=S) with PMe 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Monitoring Airspace Complexity and Determining Contributing Factors

The national airspace has evolved over many years to accommodate increased traffic demand [1] while simultaneously maintaining one of the safest forms of transportation [2], [3]. One of the reasons for this success is the ability of the system and the operators to adapt and accommodate to situations that routinely disrupt optimal operations. These situations may include: adverse weather, delays, early arrivals, equipment outages, and other factors that are outside the operators ability to control. These factors can lead to states where automation is unable to properly handle these issues and therefore air traffic controllers and pilots have to intervene, ultimately increasing communication between operators resulting in higher workload. As controller workload increases to handle sub-optimal operating conditions this can be viewed as an increase in complexity. The reasoning for this is because humans are now required to make tactical decisions in response to external factors, resulting in a departure from the strategic plan where operations would be more efficiently managed. Human operators control airspace complexity under rigid regulations that are constantly changing. The airspace is divided into sectors and the number of aircraft assigned to each controller is limited for safe handling. There has been past work that devised airspace complexity metrics in commercial aviation and related these metrics to controller workload (e.g., [4],[5]). The upper bounds on the system load are pre-determined. Such bounds on complexity make for a safe system, but the system cannot scale and adapt to autonomous, dense, and heterogeneous traffic, including the many types of Unmanned Aerial Vehicles (UAVs) envisioned to be added to the operations. We hypothesize that, as traffic density and heterogeneity grow, and other key metrics change, there will be phase transitions at which the way traffic should be managed changes significantly [6]. We offer a method for in-time detection of contributing factors that lead to phase transitions, characterized by increased complexity. To the best of our knowledge, there is no tool similar to our proposed effort that identifies such contributing factors or precursor patterns. To define the scope we are proposing to measure complexity from the viewpoint of the Terminal Radar Approach Control Facilities (TRACON) controller’s perspective. In particular we are analyzing arrivals into KSFO. With safety as the top concern for airspace operators, it is important to recognize that as density and heterogeneity grow, the focus of the system will change. Times of the day when the airspace has low density and heterogeneity, the flights will follow more efficient paths where the aircraft move on established routes that are more or less directly to the destination. However, when density and heterogeneity increases, the system will begin changing focus to avoiding conflicts and collisions and route the flights in a more flexible way. Higher flexibility requires more communication and coordination between controllers and pilots which the current automation is unable to handle. This paper proposes a novel approach that monitors airspace complexity at multiple scales, uses a Machine Learning-based tool that predicts when operations will transition to a regime of greater complexity, and identifies actions that can reduce the complexity while still maintaining efficient and safe operations. We demonstrate our proposed approach using data from multiple complementary sources. This includes, but is not limited to: historical aircraft surveillance data from NASA’s Sherlock Data Warehouse [7], METAR weather data, and airport configuration data from Aviation System Performance Metrics (ASPM). The surveillance data flight paths are sampled at a variable sample rate — increasing as the aircraft approaches the airport. This is due to how Sherlock manages flight track stitching between different radar facilities which have different sampling rates. The weather and performance data are logged at defined intervals throughout the day at a courser refresh rate. In addition to the logged data and metrics, we leverage pre-defined Standard Terminal Arrival Routes (STARs) procedures to characterize the path of each flight. Each flight files for one of these routes in the flight plan well before entering the terminal airspace, and approximately follows the route until it leaves the STAR, typically on the final fix of a runway transition. However, most flights do not always fly the full STAR procedure to completion [8], but the majority do adhere to the fixes within the common route of the procedure. Our approach leverages fixes in the common route of each of the STARs to build a reference path to the airport. This allows us to characterize the flight paths in what we are defining as the “maneuvering area” (the airspace between the STAR and before the flight is lined up on the runway’s final approach) to determine how off nominal the flights are to calculate its complexity score. Determining airspace complexity is a concept that does not have a concrete answer. In designing this metric, we consider what increases the workload for the air traffic controllers. Consequently more specialized vectoring maneuvers results in higher workload. Accordingly, we start with a theory: each flight has a direct path it takes from the STAR’s common route to the final approach’s outer marker fix for the flight’s landing runway. It is important to note that the direct path is only used as a reference. If the majority of the flights have a large consistent offset as compared to other routes it does not necessarily mean that those flights have higher complexity. We are merely building a distribution based on this direct path for that particular STAR and runway pair to determine the normal mode of operations for that route. Flights that are in the upper tail of these distributions will result in higher complexity scores and flights that fly in the median will represent the normal mode of operations and therefore will have lower complexity scores. Since flights following each STAR route take different paths to the airport, we have a different distribution for each STAR route and therefore can model these distributions to compute a complexity score from their respective normalized distributions. To evaluate the effectiveness of our proposed airspace complexity metric we will compare against an established approach based on trajectory clustering [9]. This unsupervised learning technique consists of the following steps: (1) identify the general maneuvering areas (waypoints) by performing $\kappa$-means or DBSCAN clustering on locations where aircraft frequently turn based on the surveillance radar track data, (2) map flight trajectories onto sequences of waypoints, and (3) cluster the sequences based on their common subsequences. From a high-level perspective, this baseline model learns nominal operations in the airspace through the sequence of waypoints that are representative of where aircraft change direction and defines deviations from the nominal operations as “complex.” Therefore, more deviations from the nominal operations correspond to higher complexity values. For our validation, we re-implemented this technique and tune model hyper-parameters to correctly detect waypoints for the arrival traffic into the San Francisco bay area. We will compute the complexity measure over a one-year period using our proposed technique as well as the baseline. Our validation will be based on each technique’s ability to detect a set of undesirable outcomes (e.g., go-arounds, holding patterns, average time in the airspace, etc.). Since our current complexity metric is derived from the offset from the direct reference path, it’s important to understand what causes these offsets. In many of the flights with high offset distance, flights performing holding patterns and S turns can be observed. These maneuvering tactics are utilized to add distance between the aircraft and the destination runway to prevent multiple flights from having conflicting arrival times. In order to predict a rise in complexity (or the precursor to complexity), it’s necessary to be able to identify these potential conflicts (which in turn, result in higher offsets). To do this, we define a “representative flight” for each STAR route and runway pair. This flight is approximately the path the flight would take if there was a clear path with no other flights in the airspace — including the time remaining to the airport. We first identify the flights for a given STAR runway pair using the offset to the reference path distributions that fall between the 44-55 percentiles. This yields the flights that conform to the most normal mode of operation. Each of these flights is partitioned based on the percent complete from the entry point into the maneuvering areas from 0\% – 100\% complete. Then for each percent “bin”, we take the median value of the flight’s latitude/longitude coordinates, airspeed, and (non causal) time remaining to the airport to construct a lookup table for each percent complete bin on a given route. As a flight enters the maneuvering area, we can find the estimated arrival time of a flight to the airport by finding the closest point to the representative path’s percent complete bin (relative to the flight’s current position at any snapshot in the airspace) and therefore retrieve the corresponding remaining time left on the “representative path”. We assume that the flight will follow the representative path to completion when deriving these estimates. We can then compare these estimated arrival times against other flights for the same snapshot in time to identify potential conflicts. If more flights are estimated to arrive within a tolerance window than there are runways available, then we have a potential conflict. We can use this derived measure along with other factors expected to add disruption to the operation such as weather and runway configuration changes as an input to machine learning tools to detect precursors that increases in our complexity measure. This novel method will assist in uncovering insights into the contributing factors that lead to increased complexity that may allow for in-time responses to avoid reaching a high complexity state in the airspace.

complexity↗

Hydrodynamic trait coordination and cost–benefit trade‐offs throughout the isohydric–anisohydric continuum in trees

Abstract Whole‐plant hydraulic performance depends on the integrated function of trait complexes, such as embolism resistance, stomatal closure mechanisms, and root properties. The diversity of such traits produces a wide range of response strategies to both short‐term variation of environmental conditions and long‐term changes to climate and hydrological cycles. This study aims to assess the role of different emergent hydraulic trait combinations in trees' vulnerability to drought using a quantitative modelling framework. This modelling framework may be helpful in studying the influence of plant hydraulic traits independently. It will also be used to assess how different groups of traits interact to form viable hydraulic strategies in response to different environmental conditions. We use the advanced plant hydrodynamic model, finite‐difference ecosystem‐scale tree crown hydrodynamics model version 2, to resolve plant functional traits of roots, stems, and leaves and simulate the transpiration. We define a multidimensional hydraulic “strategy space” by considering a continuum of these traits to test the outcomes of different hypothetical strategies in response to environmental conditions as observed in Northern Michigan, USA. We evaluate the degree to which simulated trees suffer hydraulic failure due to cavitation or carbon deficiency in response to reduced stomatal conductance. Our results demonstrate how the relationship between plant hydraulic strategy and hydraulic safety margin emerges from trait combinations along different tissue levels. Our findings suggest that hydrodynamic models present an exciting new possibility to define and study plant traits and hydrodynamics.

Mirfenderesgi, Golnazalsadat↗

Bond-centric modular design of protein assemblies

Directional interactions that generate regular coordination geometries are a powerful means of guiding molecular and colloidal self-assembly, but implementing such high-level interactions with proteins remains challenging due to their complex shapes and intricate interface properties. Here we describe a modular approach to protein nanomaterial design inspired by the rich chemical diversity that can be generated from the small number of atomic valencies. We design protein building blocks using deep learning-based generative tools, incorporating regular coordination geometries and tailorable bonding interactions that enable the assembly of diverse closed and open architectures guided by simple geometric principles. Experimental characterization confirms the successful formation of more than 20 multicomponent polyhedral protein cages, two-dimensional arrays and three-dimensional protein lattices, with a high (10%–50%) success rate and electron microscopy data closely matching the corresponding design models. Due to modularity, individual building blocks can assemble with different partners to generate distinct regular assemblies, resulting in an economy of parts and enabling the construction of reconfigurable networks for designer nanomaterials.

Biomaterials – proteins↗

Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series

Abstract The chemistry of trivalent transplutonium ions (Am 3+ , Cm 3+ , Bk 3+ , Cf 3+ , Es 3+ …) is usually perceived as monotonic and paralleling that of the trivalent lanthanide series. Herein, we present the first extended X‐ray absorption fine structure (EXAFS) study performed on a series of aqueous heavy actinide chelates, extending past Cm. The results obtained on diethylenetriaminepentaacetic acid (DTPA) complexes of trivalent Am, Cm, Bk, and Cf show a break to much shorter metal–oxygen nearest‐neighbor bond lengths in the case of Cf 3+ . Corroborating those results, density functional theory calculations, extended to Es 3+ , suggest that the shorter Cf−O and Es−O bonds could arise from the departure of the coordinated water molecule and contraction of the ligand around the metal relative to the other [M III DTPA(H 2 O)] 2− (M=Am, Cm, Bk) complexes. Taken together, these experimental and theoretical results demonstrate inhomogeneity within the trivalent transplutonium series that has been insinuated and debated in recent years, and that may also be leveraged for future nuclear waste reprocessing technologies.

Deblonde, Gauthier J. ‐P.↗

Communication Research in Aviation and Space Operations: Symptoms and Strategies of Crew Coordination

The day-to-day operators of today's aerospace systems work under increasing pressures to accomplish more with less. They work in operational systems which are complex, technology-based, and high-risk; in which incidents and accidents have far-reaching and costly consequences. For these and other reasons, there is concern that the safety net formerly built upon redundant systems and abundant resources may become overburdened. Although we know that human ingenuity can overcome incredible odds, human nature can also fail in unpredictable ways. Over the last 20 years, a large percentage of aviation accidents and incidents have been attributed to human errors rather than hardware or environmental factors alone. A class of errors have been identified which are not due to a lack of individual, technical competencies. Rather, they are due to the failure of teams to utilize readily available resources or information in a timely fashion. These insights began a training revolution in the aviation industry called Cockpit Resource Management, which later became known as Crew Resource Management (CRM) as its concepts and applications extended to teams beyond the flightdeck. Then, as now, communication has been a cornerstone in CRM training since crew coordination and resource management largely resides within information transfer processes--both within flightcrews, and between flightcrews and the ground operations teams that support them. The research I will describe takes its roots in CRM history as we began to study communication processes in order to discover symptoms of crew coordination problems, as well as strategies of effective crew management. On the one hand, communication is often the means or the tool by which team members manage their resources, solve problems, maintain situational awareness and procedural discipline. Conversely, it is the lack of planning and resource management, loss of vigilance and situational awareness, and non-standard communications that are implicated in accidents and incidents. NASA/Ames Crew Factors researchers have been developing a model of effective crew coordination in order to understand the sources of performance breakdowns, and to develop effective solutions and interventions. Because communication is a primary mechanism by which information is received and transmitted, and because it is observable behavior, we focus on these group processes in order to identify patterns of communication that distinguish effective from less effective crew performance. Since a prime objective is to develop training recommendations for enhancing communication skills, we interpret our findings in the context of relevant task and environmental conditions, role and procedural constraints, and the normal real-time parameters of flight operations. Another research objective is to consider how communication and coordination can be enhanced through design. For example, flight deck and hardware design as well as procedural and software design may greatly influence the efficiency with which crews communicate and coordinate their work. In addition, teams and tasks may be designed, organized, and trained so that team interactions with each other are based upon appropriately shared knowledge, procedures and situation awareness. In short, we are interested in enhancing communication practices through (1) the training of specific communication skills, and (2) the design of equipment, tasks, procedures, and teams that optimize smooth, unambiguous communication processes. Two examples of communication research will be described; one in aviation and one in space operations. The first example is a high-fidelity full mission simulation study which investigates the affect of flightdeck automation on crew coordination and communication (contrasting crew performance in the DC-9 vs. MD88). Additional information is contained in the original extended abstract.

Kanki, Barbara G.↗

Risk of Impaired Control of Spacecraft/Associated Systems and Decreased Mobility Due to Vestibular/Sensorimotor Alterations Associated with Space flight

Control of vehicles and other complex systems is a high-level integrative function of the central nervous system (CNS). It requires well-functioning subsystem performance, including good visual acuity, eye-hand coordination, spatial and geographic orientation perception, and cognitive function. Evidence from space flight research demonstrates that the function of each of these subsystems is altered by removing gravity, a fundamental orientation reference, which is sensed by vestibular, proprioceptive, and haptic receptors and used by the CNS for spatial orientation, posture, navigation, and coordination of movements. The available evidence also shows that the degree of alteration of each subsystem depends on a number of crew- and mission-related factors. There is only limited operational evidence that these alterations cause functional impacts on mission-critical vehicle (or complex system) control capabilities. Furthermore, while much of the operational performance data collected during space flight has not been available for independent analysis, those that have been reviewed are somewhat equivocal owing to uncontrolled (and/or unmeasured) environmental and/or engineering factors. Whether this can be improved by further analysis of previously inaccessible operational data or by development of new operational research protocols remains to be seen. The true operational risks will be estimable only after we have filled the knowledge gaps and when we can accurately assess integrated performance in off-nominal operational settings (Paloski et al. 2008). Thus, our current understanding of the Risk of Impaired Control of Spacecraft/Associated Systems and Decreased Mobility Due to Vestibular/Sensorimotor Alterations Associated with Space flight is limited primarily to extrapolation of scientific research findings, and, since there are limited ground-based analogs of the sensorimotor and vestibular changes associated with space flight, observation of their functional impacts is limited to studies performed in the space flight environment. Fortunately, many sensorimotor and vestibular experiments have been performed during and/or after space flight missions since 1959 (Reschke et al. 2007). While not all of these experiments were directly relevant to the question of vehicle/complex system control, most provide insight into changes in aspects of sensorimotor control that might bear on the physiological subsystems underlying this high-level integrated function.

Bloomberg, Jacob J.↗

Mapped Moments to a Cartesian Grid (MMCG) Value-Added Product Report

Objective analysis (OA) is a method of mapping unstructured data to a structured grid. In the context of scanning radar data, OA is used to interpolate data in antenna coordinates (range, azimuth, and elevation) onto a regularly spaced Cartesian grid (Trapp and Doswell 2000). The U.S. Department of Energy Atmospheric Radiation Measurement (ARM) user facility’s Mapped Moments to a Cartesian Grid (MMCG) Value-Added Product (VAP) uses the Python ARM Radar Toolkit (Py-ART), a data model-driven interactive architecture for working with weather radar data, to map the data to a Cartesian grid (Helmus and Collis 2016). MMCG, with Py-ART built in, has the ability to take radar data in antenna coordinates and map the gates to a Cartesian grid using inverse distance weight functions such as Cressman (square) and Barnes (exponential), but also can filter the data during the interpolation. MMCG also allows arbitrary formulations for the radius of influence, which are matched to particular radar scanning strategies. This creates a complex parameter space for optimizing the retention of storm structure detail while minimizing artifacts. MMCG takes data processed with ARM’s Corrected Precipitation Radar Moments in Antenna Coordinates (CMAC) VAP and maps it to a Cartesian grid as the output product. A variety of fields that have been mapped to the Cartesian grid are then saved to plots to complement each grid file.

54 ENVIRONMENTAL SCIENCES↗

Pairing a Global Optimization Algorithm with EXAFS to Characterize Lanthanide Structure in Solution

Ensemble-average sampling of structures from ab initio molecular dynamics (AIMD) simulations can be used to predict theoretical extended X-ray absorption fine structure (EXAFS) signals that closely match experimental spectra. However, AIMD simulations are time-consuming and resource-intensive, particularly for solvated lanthanide ions, which often form multiple nonrigid geometries with high coordination numbers. Here, to accelerate the characterization of lanthanide structures in solution, we employed the Northwest Potential Energy Surface Search Engine (NWPEsSe), an adaptive-learning global optimization algorithm, to efficiently screen first-shell structures. As case studies, we examine two systems: Eu(NO 3 ) 3 dissolved in acetonitrile with a terpyridine ligand (terpyNO 2 ), and Nd(NO 3 ) 3 dissolved in acetonitrile. The theoretical spectra for structures identified by NWPEsSe were compared to both experimental and AIMD-derived EXAFS spectra. The NWPEsSe algorithm successfully identified the proper solvation structure for both Eu(NO 3 ) 3 (terpyNO 2 ) and Nd(NO 3 )(acetonitrile) 3 , with the calculated EXAFS signals closely matching the experimental spectra for the Eu-ligand complex and showing good similarity for the Nd salt; the better agreement with the ligand-containing structure is attributed to a less dynamic coordination environment due to the rigid ligand. The key advantage of the global optimization algorithm lies in its ability to sample the coordination environment across the potential energy surface and reduce the time required to identify structures from generally a month to within a week. Additionally, this approach is versatile and can be adapted to characterize main-group metal complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanistic Studies of Palladium-Catalyzed Aminocarbonylation of Aryl Chlorides with Carbon Monoxide and Ammonia

Mechanistic information on a reliable, palladium-catalyzed aminocarbonylation of aryl chlorides with ammonia is reported. The reaction occurs with ethylene complex 1 as catalyst, and mechanistic information was gained by isolation of catalytic intermediates and kinetic measurements, including the first mechanistic data on the oxidative addition of aryl chloride to a palladium(0) complex in the presence of CO. Arylpalladium and phenacylpalladium halide intermediates were synthesized, and kinetic measurements of the formation and reactions of these intermediates were undertaken to determine the mechanism of the oxidative addition of aryl bromides and chlorides to a Pd(0) dicarbonyl compound in the presence of CO and the mechanism of the reaction of ammonia with a Pd(II) phenacyl complex to form benzamide. The oxidative addition of aryl chlorides and aryl bromides was determined to occur with rate-limiting reaction of the haloarene with a three-coordinate Pd(0) species bearing a bidentate phosphine and one CO ligand. A primary 13 C kinetic isotope effect suggested that this step involves cleavage of the carbon-halogen bond. Here our data show that the formation of benzamide from the reaction of phenacylpalladium halide complexes with ammonia occurs by a pathway involving reversible displacement of chloride from a phenacylpalladium chloride complex by ammonia, deprotonation of the bound ammonia to form a phenacylpalladium amido complex, and reductive elimination to form the C-N bond. Consistent with this mechanism, the reaction of an aryl palladium amido complex with CO formed the corresponding primary benzamide. A catalyst deactivation pathway involving the formation of a Pd(I) dimer also was elucidated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Alkali Counterion-Dependent Crystallization of Uranium(IV)–Chloro Structural Units

The synthesis, structural characterization, and spectroscopic properties of five tetravalent uranium (U) phases including Li 6 [U 4 (μ 3 -O) 2 Cl 18 (H 2 O) 2 ]·10H 2 O (1), [U(H 2 O) 4 Cl 4 ] (2), [U(H 2 O) 4 Cl 4 ]·KCl (3), Rb 2 UCl 6 (4), and Cs 2 UCl 6 (5) are reported. Notably, a change in the U 4+ solid-state structural unit was observed based on the identity of the alkali counterion used in the synthesis. Li 1+ yielded a tetranuclear oxo-bridged cluster, [U 4 (μ 3 -O) 2 Cl 18 (H 2 O) 2 ] 6– , Na 1+ and K 1+ yielded two structurally distinct [U(H 2 O) 4 Cl 4 ] complexes, and Rb 1+ and Cs 1+ resulted in [UCl 6 ] 2– as the dominant phases. The spectroscopic properties of the compounds were analyzed using Raman and UV–vis–NIR absorption spectroscopy. The UV–vis–NIR spectra of compounds 1–5 exhibited transitions consistent with uranium in the +4 oxidation state. Clear differences in the absorption band splitting were observed and are likely attributed to differences in metal ion coordination, crystal field effects, and outer sphere interactions Overall, this work demonstrates the utility of noncovalent interactions in tuning the crystallization of various metal complexes from otherwise identical reaction solutions and provides further evidence that counterions impact the composition and structure of actinide complexes isolated in the solid state. In this way, this work affords important insight into directing and controlling the structure of actinide complexes and clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular dynamics simulations of uranyl and plutonyl cations in a task-specific ionic liquid

Ionic liquids (ILs) are a unique class of solvents with potential applications in advanced separation technologies relevant to the nuclear industry. ILs are salts with low melting points and a wide range of tunable physical properties, such as viscosity, hydrophobiciy, conductivity, and liquidus range. ILs have negligible vapor pressure, are often non-flammable, and can have high thermal stability and a wide electrochemical window, making them attractive for use in separations processes relevant to the nuclear industry. Metal salts generally have a low solubility in ILs; however, by incorporating new functional groups into the IL cation or anion that promote complexation with the metal, the solubility can be greatly increased. One such task-specific ionic liquid (TSIL) is 1-carboxy-N, N, N-trimethylglycine bis(trifluoromethylsulfonyl)imide ([Hbet][Tf 2 N]). Water, which is detrimental for electrochemical separations, is a common impurity in ILs and can coordinate with actinyl cations, particularly in ILs containing only weakly coordinating components. Understanding the behavior of actinides in TSIL/water mixtures on a molecular level is vital for designing improved separations processes. Classical molecular dynamics simulations of uranyl(VI) and plutonyl(VI) in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf 2 N]) with deprotonated Hbet (betaine) and water have been performed to understand the coordination and dynamics of the actinyl cations. We find that betaine is a much stronger ligand than water and prefers to coordinate the metal in a bidentate manner. Potential of mean force simulations yield a relative free energy for betaine coordination of approximately -120 to -90 kJ/mol in mixtures with water. As the amount of betaine coordinated to the actinide increases, the diffusion coefficient of the actinyl cation decreases. Moreover, the betaine ligand is able to bridge between two metal centers, resulting in dimeric complexes with actinide–actinide distances of ~5 Å. Potential of mean force simulations show that these structures are stable, with relative free energies of up to -40 kJ/mol. The crystal structure for [(UO 2 ) 2 (bet) 6 (H 2 O) 2 ][Tf 2 N] 4 shows that the betaine bridges between two uranium atoms to form dimeric complexes similar to those found in our simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series

The chemistry of trivalent transplutonium ions (Am 3+ , Cm 3+ , Bk 3+ , Cf 3+ , Es 3+ …) is usually perceived as monotonic and paralleling that of the trivalent lanthanide series. We present the first extended X-ray absorption fine structure (EXAFS) study performed on a series of aqueous heavy actinide chelates, extending past Cm. The results obtained on diethylenetriaminepentaacetic acid (DTPA) complexes of trivalent Am, Cm, Bk, and Cf show a break to much shorter metal–oxygen nearest-neighbor bond lengths in the case of Cf 3+ . Corroborating those results, density functional theory calculations, extended to Es 3+ , suggest that the shorter Cf-O and Es-O bonds could arise from the departure of the coordinated water molecule and contraction of the ligand around the metal relative to the other [M III DTPA(H 2 O)] 2- (M=Am, Cm, Bk) complexes. Taken together, these experimental and theoretical results demonstrate inhomogeneity within the trivalent transplutonium series that has been insinuated and debated in recent years, and that may also be leveraged for future nuclear waste reprocessing technologies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Mode Specificity in the OH + HO 2 → H 2 O + O 2 Reaction: Enhancement of Reactivity by Exciting a Spectator Mode

A reaction usually involves a few active modes while the other modes are largely preserved throughout the reaction as spectators. Excitation of an active mode is expected to promote the reaction, but depositing energy in a spectator mode typically has no effect, because of the differing ability for energy flow to the reaction coordinate. Here, we report a surprising case of mode specificity in a key radical–radical reaction OH + HO 2 → H 2 O + O 2 , where such canonical expectations fail to hold. Despite its spectator nature, the vibrational excitation of the OH reactant is shown at low collision energies to enhance the reactivity significantly. This unique effect can be attributed to the increased attraction with HO 2 due to the larger dipole of the stretched OH. At low collision energies, the stronger attraction increases the chance of capturing the reactants to form a hydrogen-bonded complex, thus of passing through the submerged barrier. The novel mechanism differs from the conventional vibrational enhancement via coupling to the reaction coordinate at the transition state, enriching our understanding of mode specificity in chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

WH2 and proline-rich domains of WASP-family proteins collaborate to accelerate actin filament elongation

WASP-family proteins are known to promote assembly of branched actin networks by stimulating the filament-nucleating activity of the Arp2/3 complex. Here, we show that WASP-family proteins also function as polymerases that accelerate elongation of uncapped actin filaments. When clustered on a surface, WASP-family proteins can drive branched actin networks to grow much faster than they could by direct incorporation of soluble monomers. This polymerase activity arises from the coordinated action of two regulatory sequences: (i) a WASP homology 2 (WH2) domain that binds actin, and (ii) a proline-rich sequence that binds profilin–actin complexes. In the absence of profilin, WH2 domains are sufficient to accelerate filament elongation, but in the presence of profilin, proline-rich sequences are required to support polymerase activity by (i) bringing polymerization-competent actin monomers in proximity to growing filament ends, and (ii) promoting shuttling of actin monomers from profilin–actin complexes onto nearby WH2 domains. Unoccupied WH2 domains transiently associate with free filament ends, preventing their growth and dynamically tethering the branched actin network to the WASP-family proteins that create it. Collaboration between WH2 and proline-rich sequences thus strikes a balance between filament growth and tethering. Our work expands the number of critical roles that WASP-family proteins play in the assembly of branched actin networks to at least three: (i) promoting dendritic nucleation; (ii) linking actin networks to membranes; and (iii) accelerating filament elongation.

Biochemistry & Molecular Biology↗