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Interstellar/Precometary Organic Material and the Photochemical Evolution of Complex Organics

During the past two decades ground-, air-, and space-based infrared spectroscopic observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the raw materials from which planets, comets and stars form. Most interstellar material is concentrated in Large molecular clouds where simple molecules are formed by dust grain and gas phase reactions. Gaseous species striking the cold (10 K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, H2, and perhaps some NH3 and H2CO, as well as more complex species including nitriles and ketones or esters. The evidence for these compounds as well as carbon rich materials such as polycyclic aromatic hydrocarbons (PAHs), microdiamonds, and amorphous carbon will be reviewed and the possible connections with comets and meteorites will be presented in the first part of the talk. The second part of the presentation will focus on interstellar/precometary ice photochemical evolution. The chemical composition and photochemical evolution of realistic interstellar/pre-cometary ice analogs containing methanol will be discussed. ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and more complex molecules. Infrared spectroscopy, H-1 and C-13 nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry demonstrate that when ices representative of interstellar grains and comets are exposed to UV radiation at low temperature a series of moderately complex organic molecules are formed in the ice including: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C(integral)N (nitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. After warming to room temperature what remains is an organic residue composed primarily of Hexamethylenetetramine (HMT, C6H12N4), with lesser amounts of polyoxymethylene related species (POMs), amides, and ketones. This is in sharp contrast to the organic residues produced by irradiating ices which do not contain methanol (unrealistic interstellar ice analogs) or thermally promoted polymerization-type reactions in unirradiated realistic ice mixtures. Here HMT is only a minor product in a residue dominated by a mixture of polyoxymethylene related species. The implications, for infrared astronomy and astrochemistry, of high concentrations of HMT in interstellar and cometary ices may be profound. The ultraviolet photolysis of HMT frozen in H20 ice produces the "XCN" band observed in the spectra of protostellar objects and laboratory ices, as well as carbon oxides and other nitriles. Thus, HMT may be a precursor of XCN in protostellar objects and a source of CN and CO in the tail of comets. Also, HMT is known to hydrolyze under acidic conditions to yield ammonia and formaldehyde as well as amino acids. Thus, HMT may have been a source of organic material delivered to the early earth by comets.

Allamandola, Lou J.↗

Proceedings of RIKEN BNL Research Center Workshop: Multi-Hadron and Nonlocal Matrix Elements in Lattice QCD (Volume 120)

Nonperturbative QCD calculations of hadronic matrix elements are needed to understand the structure of the matter in our universe and to search for physics beyond the Standard Model. Numerical lattice gauge theory is uniquely suited for this task and has reached a remarkable level of precision. However, the types of observables that are accessible in a straightforward way are limited because lattice calculations are performed with imaginary time. Traditionally, lattice QCD determinations of hadronic matrix elements have been restricted to situations with at most one stable hadron in the initial and final states, and with a single insertion of a local current. This situation has been changing recently thanks to theoretical breakthroughs and pioneering numerical studies of new observables. At this workshop, the latest developments concerning multi-hadron systems and nonlocal matrix elements in lattice QCD were discussed: • Liischer's quantization condition relates the energy spectrum of two interacting particles in a finite volume to the scattering phase shifts. At this workshop, generalizations of Liischer's quantization condition to three-particle systems, and to two-particle systems with long-range QED interactions were presented. • Advanced numerical lattice QCD studies of hadronic resonances using the Liischer method were shown, including coupled-channel scattering and near-threshold resonances. • The Lellouch-Liischer formula relates two-hadron matrix elements computed in a finite volume to the infinite-volume matrix elements. This workshop included presentations of the latest numerical lattice QCD calculations ofthe nonleptonic weak decay K ® tl tl, as well as new theoretical results extending the Lellouch-Liischer formula to general multichannel 1 ® 2 transition matrix elements. • Novel methods allowing the direct calculation of parton distribution functions in lattice QCD were discussed, and a one-loop calculation of the lattice-to-continuum matching required for these methods was presented. • Lattice QCD calculations of nonlocal matrix elements relevant for rare kaon decays and for the Kl-Ks mass difference were shown. The inclusion of QED corrections in weak decays was discussed. Results from a new method for computing the hadronic light-by-light contribution to the muon anomalous magnetic moment were shown. • • Calculations of the binding energies and magnetic moments of light nuclei directly from lattice QCD were presented. The theoretical foundations of a potential-based method for studying multihadron interactions on the lattice were discussed, and an application of this method to charmed tetraquarks was shown.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Understanding and Controlling Conductivity Transitions in Correlated Solids: Spectroscopic Studies of Electronic Structure in Vanadates (Final Report)

This research project is focused on synchrotron radiation based x-ray spectroscopic studies of the metal to insulator transition in vanadium oxides. In doing so, we developed a fundamental understanding of the origins of conductivity transitions in correlated electron materials. Conductivity transitions can be driven by external and internal mechanisms, including electric and magnetic fields, chemical doping, defects, disorder, pressure, dimensionality, and temperature. Vanadium oxides, and vanadium dioxide in particular, display particularly complex electronic phenomena. Binary vanadium oxides, and ternary oxides with substituted metal cations, exhibit a broad range of complex conductivity transitions, as well as charge ordering transitions, structural phase transitions, frustrated spin structures, superconductivity, and unusual magnetic properties. As such, vanadates are a prototypical class of correlated material, where fundamentally important physical themes can be explored, both experimentally and theoretically. The experimental tools used were soft x-ray emission spectroscopy (XES), soft x-ray absorption spectroscopy (XAS), resonant inelastic soft x ray scattering (RIXS), x-ray photoemission spectroscopy (XPS), angle resolved photoemission spectroscopy (ARPES), and spectroscopic photoemission low energy electron microscopy (SPELEEM). This broad range of techniques delivered data that was used to understand the electronic structure in these oxides. Vanadium oxides as single crystals, thin films, polycrystalline powders, and nanoparticles were studied to determine the influence of the physical structure the materials properties. A rich and varied selection of experiments were performed, and by combining the information gathered by our x-ray spectroscopic techniques, we developed a comprehensive understanding of electronic structure in vanadium oxides. We measured band structures and Fermi surfaces, studied the coupling between collective excitations and quasi-particles, measured the local, site and element specific electronic structure, as well as the cation charge state, measured orbital hybridization, and measured element specific low energy valence excitations such as dd* and charge transfer excitations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Observations in the vicinity of substorm onset: Implications for the substrom process

Multi-instrument data sets from the ground and satellites at both low and high altitude have provided new results concerning substorm onset and its source region in the magnetosphere. Twenty-six out of 37 substorm onset events showed evidence of azimuthally spaced auroral forms (AAFs) prior to the explosive poleward motion associated with optical substorm onset. AAFs can span 8 hours of local time prior to onset and generally propagate eastward in the morning sector. Onset itself is, however, more localized spanning only about 1 hour local time. AAF onset occur during time periods when the solar wind pressure is relatively high. AAFs brighten in conjunction with substorm onset leading to the conclusion that they are a growth phase activity casually related to substorm onset. Precursor activity associated with these AAFs is also seen near geosynchronous orbit altitude and examples show the relationship between the various instrumental definitions of substorm onset. The implied mode number (30 to 135) derived from this work is inconsistent with cavity mode resonances but is consistent with a modified flute/ballooning instability which requires azimuthal pressure gradients. The extended source region and the distance to the open-closed field line region constrain reconnection theory and local mechanisms for substorm onset. It is demonstrated that multiple onset substorms can exist for which localized dipolarizations and the Pi 2 occur simultaneously with tail stretching existing elsewhere. These pseudobreakups can be initiated by auroral streamers which originate at the most poleward set of arc systems and drift to the more equatorward main UV oval. Observations are presented of these AAFs in conjunction with low- and high-altitutde particle and magnetic field data. These place the activations at the interface between dipolar and taillike field lines probably near the peak in the cross-tail current. These onsets are put in the context of a new scenario for substorm morphology which employs individual modules which operate independently or couple together. This allows particular substorm events to be more accurately described and investigated.

Elphinstone, R. D.↗

Global gyrokinetic stability of collisionless microtearing modes in large aspect ratio tokamaks

Linear full radius gyrokinetic calculations show the existence of unstable microtearing modes (MTMs) in purely collisionless, high temperature, large aspect ratio tokamak plasmas. The present study takes into account fully gyrokinetic highly passing ions and electrons. The global 2-D structures of the collisionless mode with full radius coupling of the poloidal modes is obtained and compared with another electromagnetic mode, namely, the Alfvén Ion Temperature Gradient (AITG) mode (or Kinetic Ballooning Mode, KBM) for the same equilibrium profile. Several important characteristics of the modes are brought out and compared, such as a clear signature in the symmetry properties of the two modes, the plasma–β dependence, and radial and poloidal length scales of the electrostatic and magnetic vector potential fluctuations. Extensive parameter scans for this collisionless microtearing mode reveal the scaling of the growth rate with β and the electron temperature gradient η{sub e}. Scans at different β values show an inverse relationship between the η{sub e} threshold and β, leading to a stability diagram, and implying that the mode might exist at moderate to strong temperature gradients for finite β plasmas in large aspect ratio tokamaks. In contrast to small aspect ratio tokamaks where the trapped electron magnetic drift resonance is found to be important, in large aspect ratio tokamaks, a strong destabilization due to the magnetic drift resonance of passing electrons is observed and is identified as a possible collisionless drive mechanism for the collisionless MTM.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Overdamped antiferromagnetic strange metal state in Sr3IrRuO7

The unconventional electronic ground state of Sr 3 IrRuO 7 is explored via resonant x-ray scattering techniques and angle-resolved photoemission measurements. As the Ru content approaches x = 0.5 in Sr 3 (Ir 1-x Ru x ) 2 O 7 , intermediate to the J eff = 1/2 Mott state in Sr 3 Ir 2 O 7 and the quantum critical metal in Sr 3 Ru 2 O 7 , a thermodynamically distinct metallic state emerges. The electronic structure of this intermediate phase lacks coherent quasiparticles, and charge transport exhibits a linear temperature dependence over a wide range of temperatures. Spin dynamics associated with the long-range antiferromagnetism of this phase show nearly local, overdamped magnetic excitations and an anomalously large energy scale of 200 meV-an energy far in excess of exchange energies present within either the Sr 3 Ir 2 O 7 or Sr 3 Ru 2 O 7 solid-solution end points. Overdamped quasiparticle dynamics driven by strong spin-charge coupling are proposed to explain the incoherent spectral features of the strange metal state in Sr 3 IrRuO 7 .

36 MATERIALS SCIENCE↗

Self-consistent Model of Magnetospheric Electric Field, RC and EMIC Waves

Electromagnetic ion cyclotron (EMIC) waves are an important magnetospheric emission, which is excited near the magnetic equator with frequencies below the proton gyro-frequency. The source of bee energy for wave growth is provided by temperature anisotropy of ring current (RC) ions, which develops naturally during inward convection from the plasma sheet These waves strongly affect the dynamic s of resonant RC ions, thermal electrons and ions, and the outer radiation belt relativistic electrons, leading to non-adiabatic particle heating and/or pitch-angle scattering and loss to the atmosphere. The rate of ion and electron scattering/heating is strongly controlled by the Wave power spectral and spatial distributions, but unfortunately, the currently available observational information regarding EMIC wave power spectral density is poor. So combinations of reliable data and theoretical models should be utilized in order to obtain the power spectral density of EMIC waves over the entire magnetosphere throughout the different storm phases. In this study, we present the simulation results, which are based on two coupled RC models that our group has developed. The first model deals with the large-scale magnetosphere-ionosphere electrodynamic coupling, and provides a self-consistent description of RC ions/electrons and the magnetospheric electric field. The second model is based on a coupled system of two kinetic equations, one equation describes the RC ion dynamics and another equation describes the power spectral density evolution of EMIC waves, and self-consistently treats a micro-scale electrodynamic coupling of RC and EMIC waves. So far, these two models have been applied independently. However, the large-scale magnetosphere-ionosphere electrodynamics controls the convective patterns of both the RC ions and plasmasphere altering conditions for EMIC wave-particle interaction. In turn, the wave induced RC precipitation Changes the local field-aligned current distributions and the ionospheric conductances, which are crucial for a large-scale electrodynamics. The initial results from this new self-consistent model of the magnetospheric electric field, RC and EMIC waves will be shown in this presentation.

Gamayunov, K. V.↗

Bis-(2-Hydroxybenzylidene)-1H-Pyrazole 3,5-Dicarbohydrazide as a Novel Chemosensor for the Detection of Endogenous Zinc: A Fluorometric Study

The study reports synthesis and photophysical studies of a new zinc sensing pyrazole scaffold structurally characterized to be bis(2-hydroxybenzylidene)-1H-pyrazole-3,5-dicarbohydrazide (PHSA). Excitation of the probe at 330 nm results in an emission band at 417 nm which ratiometrically red shifts to 466 nm upon Zn{sup 2+} addition in an unprecedented way. The photo induced electron transfer (PET) coupled intramolecular charge transfer (ICT) working for a dual-channel fluorescence emission pathway is observed and studies were supported with density functional theory and NMR titration experiments. The probe exhibited dissociation constant of 1.2156 and detection limit as low as 992 nM. The cytotoxic effects of the probe on 60 tumour cell lines were tested. The intracellular zinc sensing with reversible binding potential is verified with fluorescence microscopy experiment.

74 ATOMIC AND MOLECULAR PHYSICS↗

Obtaining Stokes Parameters from the SUMI Experiment

A sounding rocket experiment designed at the Marshall Space Flight Center, named the Solar Ultraviolet Magnetograph Investigation, had its second launch in July of 2012 to test the feasibility of measuring polarization signals of the ionized magnesium resonance doublet near 280 nm, originating from the transition region. The rocket housed a telescope at the front end and an imaging system at the rear end. Placed at the focal point of the self‐filtering telescope, a wave plate rotated through 12 predefined angular orientations to restrict the measurements to specific combinations of circular and linear polarization. Coupled with a double Wollaston analyzer, the linearly polarized ordinary and extraordinary beams were measured for the 12 combinations, each containing different fractions of the Stokes parameters (I, Q, U, V). A thorough analysis of the data has allowed us to come to several conclusions regarding the design of the experiment. 1) We are confident that polarization can be measured. A sunspot region was determined to exhibit similar results over multiple pixels. 2) Measurements are limited by resolution, i.e. regions smaller than the angular resolution per pixel cannot be resolved with any certainty. 3) Temporal evolution of magnetic features must be considered in future experimental designs. Measurements need to be taken in repeated cycles as opposed to a single cycle over the duration of the experiment. In our presentation, we will provide a summary of the observations along with the methods of our analysis, including the limitations that we've encountered.

Fayock, Brian↗

Donor–Acceptor Conjugated Copolymers Containing Transition-Metal Complex: Intrachain Magnetic Exchange Interactions and Magneto-Optical Activity

A donor-acceptor conjugated copolymer containing thienothiophene (TT) (Donor) units and Co(II) complexes (Acceptor) has been synthesized and characterized. The studies of magnetic properties of the polymers by SQUID and EPR measurements showed antiferromagnetic exchange interaction between neighboring spin centers along with the polymer backbone through intrachain in-teractions. It is the first time that D-A conjugated polymer backbone serving as bridging ligands for magnetic couplings, making this type of polymers promising as magnetic materials. Moreover, the magneto-optical activity (MOA) of polymer LCP1 was char-acterized using magnetic circular dichroism (MCD) spectroscopy. It was found that the material exhibits a large magneto-optic rotation with a peak Verdet constant of 2980 deg*T -1 *m -1 at 590 nm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetoelastic Waves in Submicron Yttrium–Iron Garnet Films Manufactured by Means of Ion-Beam Sputtering onto Gadolinium–Gallium Garnet Substrates

A series of equidistant oscillations have been revealed in the transmission spectrum and dispersion law of Damon–Eshbach surface magnetostatic waves (SMSWs) propagating in submicron (200-nm) yttrium–iron garnet (YIG) films manufactured by means of ion-beam sputtering onto gadolinium–gallium garnet (GGG) substrates. These oscillations correspond to the excitation of magnetoelastic waves in the YIG–GGG structure at frequencies of resonant interaction between the surface magnetostatic waves and the elastic shear modes of the wave-guiding YIG–GGG structure. The obtained results show that the studied YIG films are characterized by an efficient magnetoelastic coupling between their spin and elastic subsystems and the matching of acoustic impedances at the YIG–GGG interface, thus providing the possibility to consider the ion-beam sputtering of YIG films onto GGG substrates as a promising technology for the creation of magnonic and straintronic devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Coherent transfer of nuclear spin polarization in field-cycling NMR experiments

Coherent polarization transfer effects in a coupled spin network have been studied over a wide field range. The transfer mechanism is based on exciting zero-quantum coherences between the nuclear spin states by means of non-adiabatic field jump from high to low magnetic field. Subsequent evolution of these coherences enables conversion of spin order in the system, which is monitored after field jump back to high field. Such processes are most efficient when the spin system passes through an avoided level crossing during the field variation. The polarization transfer effects have been demonstrated for N-acetyl histidine, which has five scalar coupled protons; the initial spin order has been prepared by applying RF-pulses at high magnetic field. The observed oscillatory transfer kinetics is taken as a clear indication of a coherent mechanism; level crossing effects have also been demonstrated. The experimental data are in very good agreement with the theoretical model of coherent polarization transfer. The method suggested is also valid for other types of initial polarization in the spin system, most notably, for spin hyperpolarization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

27 AlNMR chemical shift of Al(OH)$^{-}_{4}$ calculated from first principles: Assessment of error cancellation in chemically distinct reference and target systems

Predicting accurate nuclear magnetic resonance chemical shieldings relies upon cancellation of different types of errors between the theoretically calculated shielding constant of the analyte of interest and the reference. Often, the intrinsic error in computed shieldings due to basis sets, approximations in the Hamiltonian, description of the wave function, and dynamic effects is nearly identical between the analyte and reference, yet if the electronic structure or sensitivity to local environment differs dramatically, this cannot be taken for granted. Detailed prior work has examined the octahedral trivalent cation Al(H 2 O)$^{3+}_{6}$, accounting for ab initio intrinsic errors. However, the use of this species as a reference for the chemically distinct tetrahedral anion Al(OH)$^{-}_{4}$ requires an understanding of how these errors cancel, in order to define the limits of accurately predicting 27 Al chemical shielding in Al(OH)$^{-}_{4}$. In this work, we estimate the absolute shielding of the 27 Al nucleus in Al(OH)$^{-}_{4}$ at the coupled cluster level (515.1± 5.3 ppm). Shielding sensitivity to the choice of method approximation and atomic basis sets used has been evaluated. Solvent and thermal effects are assessed through ensemble averaging techniques using ab-initio molecular dynamics. The contribution of each type of intrinsic error is assessed for the Al(H 2 O)$^{3+}_{6}$ and Al(OH)$^{-}_{4}$ ions, revealing significant differences that fundamentally hamper the ability to accurately calculate the 27 Al chemical shift of Al(OH)$^{-}_{4}$ from first principles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigation of mode activity in NBI-heated experiments of Wendelstein 7-X

The 2018 operation phase (OP 1.2b) of the stellarator Wendelstein 7-X (W7-X) included, for the first time, neutral beam injection (NBI) to heat the plasma. Since the injection geometry at W7-X is not parallel, this generates both passing and trapped fast particles. During longer phases of NBI injection, with the primary purpose to study the heating efficiency of this system, Alfvén eigenmodes (AEs) were observed by a number of diagnostics, including the phase contrast imaging (PCI) system, the magnetic pick-up coils (Mirnov coils), and the soft x-ray multi-camera tomography system (XMCTS). Alfvén eigenmodes are of great interest for future fusion reactors as it has been shown that the resonant interaction of fast ions with self-excited AEs can lead to enhanced transport of fast ions and potentially to energy losses. This is especially true for so-called gap-modes, Alfvén eigenmodes with frequencies in gaps of the continuous spectrum, since they lack continuum damping. These modes are commonly known to be excited by fast ions, but other destabilizing mechanisms, e.g. the electron-pressure gradient are also possible. In this article we present a first analysis of the experimentally observed frequencies from the theoretical side. The calculation of shear Alfvén wave continua for selected cases and the assignment of observed frequencies to the gaps of the continuous spectra are presented. Using the ideal-MHD code CKA (Könies A. 2007 10th IAEA TM on Energetic Particles in Magnetic Confinement System), we find gap modes that match the experimental measurements in terms of the observed frequencies. We emphasize the crucial roles played by the coupling of sound and Alfvén waves as well as of the Doppler shift arising as a consequence of the radial electric field in W7-X. We employ the perturbative gyrokinetic code CKA-EUTERPE (Feh´er 2013 Simulation of the interaction between Alfv´en waves and fast particles), using a slowing-down distribution function for the fast ions as calculated by the Monte-Carlo particle following code ASCOT (Hirvijoki et al 2014 Comput. Phys. Commun. 185 1310–21) to assess the fast-ion drive. Here we find that the fast-ion drive is insufficient to overcome the background-plasma damping. The fact that unstable modes were observed experimentally may point to problems with the modelling or indicate the existence of other destabilizing mechanisms, e.g. associated with the electron-pressure gradient (Windisch et al 2017 Plasma Phys. Control. Fusion 59 105002) that sensitively depend on the profiles of the background plasma.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Impact of n > 1 neoclassical tearing modes on fast ions, plasma rotation, and the onset of disruptive tearing modes in DIII-D ITER baseline scenario

We present integrated TRANSP-kick analyses quantitatively characterizing how n > 1 magnetic islands redistribute fast ions (FIs) and modify momentum balance in low-torque DIII-D H-mode scenarios operated with the ITER normalized parameter set and shape (ITER baseline scenario, or IBS). In this plasma scenario, disruptive neoclassical tearing modes (NTMs) are most commonly seeded by nonlinear 3-wave coupling when the differential rotation between the q = 1 and q = 2 surfaces ($δf_{1, 2}$) approaches zero. Analysis of a DIII-D IBS database of shots unstable to the 2/1 NTM demonstrates that the flattening rotation profile is correlated with n > 1 NTM amplitude growth, with a strong drop in $δf_{1, 2}$ occurring when the radial magnetic perturbation amplitude at the rational surface ($δB$ r s ) is estimated to be about 20 G. The interpretive TRANSP-kick simulations show that the experimentally observed reduction in core rotation is due to the fast-ion kicks. Nonlinearity in momentum losses versus NTM amplitude is found to be correlated with overlap of FI island chains, occurring when $δB$ r s is about 35 G, in rough agreement with the experimental results. This agreement suggests the primary mechanism for the conductive momentum loss in the core is due to chaotic FI orbits and FI losses developing from overlapping resonant FI island chains.

ITER baseline scenario↗

Recent Progress on the VASIMR Engine

The development of the Variable Specific Impulse Magnetoplasma Rocket (VASIMR) was initiated in the late 1970s to address a critical requirement for fast, high-power interplanetary space transportation. Its high-power and electrodeless design arises from the use of radio frequency (RF) waves to create and accelerate plasma in a magnetic nozzle. While not being a fusion rocket, it borrows heavily from that technology and takes advantage of the natural topology of open-ended magnetic systems. In addition the system lends itself well for Constant Power Throttling (CPT,) an important ability to vary thrust and specific impulse, over a wide operational range, while maintaining maximum power. This allows in-flight mission-optimization of thrust and specific impulse to enhance performance and reduce trip time. A NASA-led, research team, involving industry, academia and government facilities is pursuing the development of this concept in the United States. The technology can be validated, in the near term, in venues such as the International Space Station, where it can also serve as both a drag compensation device and a plasma contactor for the orbital facility. Recent advances in the development of this technology involve the demonstration of efficient propellant utilization in a flowing helicon plasma discharge as well as the experimental verification of single-pass ion acceleration, as predicted by theory I, by coupling RF power to the plasma through ion cyclotron resonance. This paper outlines these and other progress in our understanding of VASIMR physics and presents the concepts for its potential application in NASA's new vision of space exploration.

Chang-Diaz, F. R.↗

Synthesis, Characterization, and Water Oxidation Activity of Isomeric Ru Complexes

The synthesis and characterization of the isomeric ruthenium complexes with the general formula cis- and trans-[Ru(trpy)(qc)X] n+ (trpy is 2,2':6',2"-terpyridine, qc is 8-quinolinecarboxylate, cis-1 and trans-1, X = Cl, n = 0; cis-2 and trans-2, X=OH2, n = 1) with respect to the relative disposition of the carboxylate and X ligands are reported. For comparison purposes, another set of ruthenium complexes with general formula cis- and trans-[Ru(trpy)(pic)(OH 2 )]+ (pic is 2-picolinate (cis-3, trans-3)) have been prepared. The complexes with a qc ligand show a more distorted geometry compared to the complexes with a pic ligand. In all of the cases, the trans isomers show lower potential values for all of the redox couples relative to the cis isomers. Furthermore, complexes cis-2 and trans-2 with six-member chelate rings show higher catalytic activity than cis-3 and trans-3. Overall, it was shown that the electronic perturbation to the metal center exerted by different orientation and geometry of the ligands significantly influences both redox properties and catalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamics-based selective 2D {sup 1}H/{sup 1}H chemical shift correlation spectroscopy under ultrafast MAS conditions

Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of {sup 1}H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of {sup 1}H/{sup 1}H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗