Odd electron species are important intermediates in organometallic chemistry, participating in a variety of catalytic and electron-transfer reactions which produce stable even-electron products. While electron deficient 17-electron (17e) radicals have been well characterized, the possible existence of short-lived 19-electron (19e) radicals has been a subject of continuing investigation. 19e radicals have been postulated as intermediates in the photochemical ligand substitution and disproportionation reactions of organometallic dimers containing a single metal-metal bond, yet the reactions of these intermediates on diffusion-limited time scales (ns-{micro}s) have never been directly observed. This study resolves the 19e dynamics in the ligand substitution of 17e radicals CpW(CO){sub 3}{sup {sm_bullet}} (Cp = C{sub 5}H{sub 5}) with the Lewis base P(OMe){sub 3}, providing the first complete description 19e reactivity.

The 2004 Gordon Conference on Donor/Acceptor Interactions will take place at Salve Regina University in Newport, Rhode Island on August 8-13, 2004. The conference will be devoted to the consequences of charge interaction and charge motion in molecular and materials systems.

We present a novel approach to reconstructing the projected mass distribution from the sparse and noisy weak gravitational lensing shear data. The reconstructions are regularized via the knowledge gained from numerical simulations of clusters, with trial mass distributions constructed from n NFW profile ellipsoidal components. The parameters of these ''atoms'' are distributed a priori as in the simulated clusters. Sampling the mass distributions from the atom parameter probability density function allows estimates of the properties of the mass distribution to be generated, with error bars. The appropriate number of atoms is inferred from the data itself via the Bayesian evidence, and is typically found to be small, reecting the quality of the data. Ensemble average mass maps are found to be robust to the details of the noise realization, and succeed in recovering the demonstration input mass distribution (from a realistic simulated cluster) over a wide range of scales. As an application of such a reliable mapping algorithm, we comment on the residuals of the reconstruction and the implications for predicting convergence and shear at specific points on the sky.

Decagonal quasicrystals are made of pairs of atomic planes with pentagonal symmetry periodically stacked along a 10-fold axis. We have investigated the atomic structure of the 2-fold surface of a decagonal Al-Ni-Co quasicrystal using scanning tunneling microscopy (STM). The surface consists of terraces separated by steps of heights 1.9, 4.7, 7.8, and 12.6{angstrom} containing rows of atoms parallel to the 10-fold direction with an internal periodicity of 4{angstrom}. The rows are arranged aperiodically, with separations that follow a Fibonacci sequence and inflation symmetry. The results indicate that the surfaces are preferentially Al-terminated and in general agreement with bulk models.

A Service Class Description (SCD) is an effective meta-data based approach for discovering Deep Web sources whose data exhibit some regular patterns. However, it is tedious and error prone to create an SCD description manually. Moreover, a manually created SCD is not adaptive to the frequent changes of Web sources. It requires its creator to identify all the possible input and output types of a service a priori. In many domains, it is impossible to exhaustively list all the possible input and output data types of a source in advance. In this paper, we describe machine learning approaches for automatic generation of the data types of an SCD. We propose two different approaches for learning data types of a class of Web sources. The Brute-Force Learner is able to generate data types that can achieve high recall, but with low precision. The Clustering-based Learner generates data types that have a high precision rate, but with a lower recall rate. We demonstrate the feasibility of these two learning-based solutions for automatic generation of data types for citation Web sources and presented a quantitative evaluation of these two solutions.

Super B-factory designs under consideration expect to reach luminosities in the 10{sup 35}-10{sup 36} range. The dramatic luminosity increase relative to the existing B-factories is achieved, in part, by raising the beam currents stored in the electron and positron rings. For such machines to succeed it is necessary to consider in the RF system design not only the gap voltage and beam power, but also the beam loading effects. The main effects are the synchronous phase transients due to the uneven ring filling patterns and the longitudinal coupled-bunch instabilities driven by the fundamental impedance of the RF cavities. A systematic approach to predicting such effects and for optimizing the RF system design will be presented. Existing as well as promising new techniques for reducing the effects of heavy beam loading will be described and illustrated with examples from the PEP-II and the KEKB.

Upon cooling a Pu-2.0 at% Ga alloy from the ambient temperature, the metastable delta phase partially transforms martensitically to the alpha-prime phase. Because this transformation involves a 25% volume contraction, plastic accommodation by the delta matrix must occur. When the material is isochronally heated or isothermally annealed above ambient temperatures, the reversion of alpha-prime to delta is likely to occur by the alpha-prime/delta interface moving to consume the alpha-prime particles. This reversion exhibits a burst martensitic mode and is observed as sharp spikes in differential scanning calorimetry data and as steps in resistometry data. These large bursts appear to be the result of an interplay between the autocatalytically driven transformation of individual alpha-prime particles and self-quenching caused by small changes in temperature and/or stress accompanying each burst. The behavior of this Pu-Ga alloy is compared to that of a steel referred to as a ''burst martensite'' in the literature, which also exhibits bursts during both thermal cycling and isothermal holds.

The caustic precipitation of plutonium (Pu) and uranium (U) from Pu and U containing waste solutions has been investigated to determine whether gadolinium (Gd) could be used as a neutron poison for precipitation with greater than a fissile mass containing both Pu and enriched U. Precipitation experiments were performed using both actual samples and simulant solutions with a range of 2.6-5.16 g/L U and 0-4.3 to 1 U to Pu. Analyses were performed on solutions at intermediate pH to determine the partitioning of elements for accident scenarios. When both Pu and U were present in the solution, precipitation began at pH 4.5 and by pH 7, 99 percent of Pu and U had precipitated. When complete neutralization was achieved at pH greater than 14 with 1.2 M excess OH-, greater than 99 percent of Pu, U, and Gd had precipitated. At pH greater than 14, the particles sizes were larger and the distribution was a single mode. The ratio of hydrogen to fissile atoms in the precipitate was determined after both settling and centrifuging and indicates that sufficient water was associated with the precipitates to provide the needed neutron moderation for Gd to prevent a criticality in solutions containing up …

A detailed chemical kinetic modeling approach is used to examine the phenomenon of suppression of sooting in diesel engines by addition of oxygenated hydrocarbon species to the fuel. This suppression, which has been observed experimentally for a few years, is explained kinetically as a reduction in concentrations of soot precursors present in the hot products of a fuel-rich diesel ignition zone when oxygenates are included. Oxygenates decrease the overall equivalence ratio of the igniting mixture, producing higher ignition temperatures and more radical species to consume more soot precursor species, leading to lower soot production. The kinetic model is also used to show how different oxygenates, ester structures in particular, can have different soot-suppression efficiencies due to differences in molecular structure of the oxygenated species.

Measurements of the angles and sides of the unitarity triangle and of the rates of rare B meson decays are crucial for the precise determination of Standard Model parameters and are sensitive to the presence of new physics particles in the loop diagrams. In this paper the recent measurements performed in this area by BABAR and Belle will be presented. The direct measurement of the angle {alpha} is for the first time as precise as the indirect determination. The precision of the |V{sub ub}| determination has improved significantly with respect to previous measurement. New limits on B {yields} {tau}{nu} decays are presented, as well as updated measurements on b {yields} s radiative transitions and a new observation of b {yields} d{gamma} transition made by Belle.

Atomistic simulations of alloys at the classic--or empirical--level face the challenge to correctly model basic thermodynamic properties. In this work we propose a methodology to generalize many-body classic potentials to incorporate complex formation energy curves. Application to Fe-Cr allows us to correctly predict the order vs segregation tendency in this alloy, as observed experimentally and calculated with ab initio techniques, providing in this way a potential suitable for radiation damage studies.

High power microwave sources at X-Band, delivering 400 to 500 of megawatts for about 400 ns, have been recently developed. These sources can power a microwave undulator with short period and large gap, and can be used in short wavelength FELs reaching the nm region at a beam energy of about 1 GeV. We present here an experiment designed to demonstrate that microwave undulators have the field quality needed for high gain FELs.

We point out that current experimental data for partial B {yields} {pi}l{nu} branching fractions reduce the theoretical input required for a precise extraction of |V{sub ub}| to the form-factor normalization at a single value of the pion energy. Different parameterizations of the form factor shape leading to this conclusion are compared and the role of dispersive bounds on heavy-to-light form factors is clarified.

Genome features of the Bacillus cereus group genomes (representative strains of Bacillus cereus, Bacillus anthracis and Bacillus thuringiensis sub spp israelensis) were analyzed and compared with the Bacillus subtilis genome. A core set of 1,381 protein families among the four Bacillus genomes, with an additional set of 933 families common to the B. cereus group, was identified. Differences in signal transduction pathways, membrane transporters, cell surface structures, cell wall, and S-layer proteins suggesting differences in their phenotype were identified. The B. cereus group has signal transduction systems including a tyrosine kinase related to two-component system histidine kinases from B. subtilis. A model for regulation of the stress responsive sigma factor sigmaB in the B. cereus group different from the well studied regulation in B. subtilis has been proposed. Despite a high degree of chromosomal synteny among these genomes, significant differences in cell wall and spore coat proteins that contribute to the survival and adaptation in specific hosts has been identified.

One of the scientific objectives of the ARM Tropical Warm Pool International Cloud Experiment (TWPICE) planned for early 2006 at Darwin, Australia is to describe convection characteristics and its interaction with the large-scale fields. In view of the short duration of the experiment, it is important to determine the long-term statistics of convection and its associated clouds from the observations and global climate models (GCM) so as to put the experiment results in proper climate perspective. For this purpose, we examine several important fields associated with the characteristics of convection and the relationships between convection and clouds using GCM simulations and available satellite and surface observations. These include the seasonal variation of convection, the relationships between convection and the upper-level cloud amount, cloud ice water content and cloud radiative forcing. One major goal of the ARM program is to improve GCM cloud and convection parameterizations. Using NCAR Community Atmosphere Model (CAM3), we demonstrate that GCM simulations in the tropical western Pacific including Darwin can be significantly improved by improving convection parameterization.

The complete genomic sequence of Pseudomonas syringae pathovar syringae B728a (Pss B728a), has been determined and is compared with that of Pseudomonas syringae pv. tomato DC3000 (Pst DC3000). The two pathovars of this economically important species of plant pathogenic bacteria differ in host range and other interactions with plants, with Pss having a more pronounced epiphytic stage of growth and higher abiotic stress tolerance and Pst DC3000 having a more pronounced apoplastic growth habitat. The Pss B728a genome (6.1 megabases) contains a circular chromosome and no plasmid, whereas the Pst DC3000 genome is 6.5 mbp in size, composed of a circular chromosome and two plasmids. While a high degree of similarity exists between the two sequenced Pseudomonads, 976 protein-encoding genes are unique to Pss B728a when compared to Pst DC3000, including large genomic islands likely to contribute to virulence and host specificity. Over 375 repetitive extragenic palindromic sequences (REPs) unique to Pss B728a when compared to Pst DC3000 are widely distributed throughout the chromosome except in 14 genomic islands, which generally had lower GC content than the genome as a whole. Content of the genomic islands vary, with one containing a prophage and another the plasmid pKLC102 of P. aeruginosa …

Lawrence Livermore National Laboratory (LLNL) uses the Cost-Effective Sampling (CES) program for reviewing groundwater data and optimizing the site's groundwater monitoring plan. The CES program produces a data assessment sheet and a lowest-frequency sampling schedule for each groundwater monitoring location. The assessment sheet and recommended sampling schedule greatly streamline the data review process and provide useful information for regulatory and remedial decision-making. The determination of sampling frequency for a given location is based on trend, variability, and magnitude statistics. The underlying principle is that a location's schedule should be determined primarily by the rate of change in concentrations observed there in the recent past. The larger the rate of change, whether upward or downward, the greater the need for frequent sampling. Conversely, where little change is observed, less sampling is recommended. In 1992, CES was approved by the U.S. EPA - Region IX and the local regulators for use at LLNL, and became part of the LLNL's approved compliance monitoring plan (Lamarre et al. 1996). Applying the CES methodology produced, initially, a 40% reduction in the annual number of required groundwater samples, and with recent optimization of the program a 55% reduction has been produced. This reduction saves LLNL $530,000 …

The Eap (extracellular adherence protein) of Staphylococcus aureus functions as a secreted virulence factor by mediating interactions between the bacterial cell surface and several extracellular host proteins. Eap proteins from different Staphylococcal strains consist of four to six tandem repeats of a structurally uncharacterized domain (EAP domain). We have determined the three-dimensional structures of three different EAP domains to 1.8, 2.2, and 1.35 {angstrom} resolution, respectively. These structures reveal a core fold that is comprised of an {alpha}-helix lying diagonally across a five-stranded, mixed {beta}-sheet. Comparison of EAP domains with known structures reveals an unexpected homology with the C-terminal domain of bacterial superantigens. Examination of the structure of the superantigen SEC2 bound to the {beta}-chain of a T-cell receptor suggests a possible ligand-binding site within the EAP domain (Fields, B. A., Malchiodi, E. L., Li, H., Ysern, X., Stauffacher, C. V., Schlievert, P. M., Karjalainen, K., and Mariuzza, R. (1996) Nature 384, 188-192). These results provide the first structural characterization of EAP domains, relate EAP domains to a large class of bacterial toxins, and will guide the design of future experiments to analyze EAP domain structure/function relationships.

We present volume, density, and tensile property change observed from both naturally and accelerated aged plutonium alloys. Accelerated alloys are plutonium alloys with a fraction of Pu-238 to accelerate the aging process by approximately 18 times the rate of unaged weapons-grade plutonium. After thirty-five equivalent years of aging on accelerated alloys, the dilatometry shows the samples at 35 C have swelled in volume by 0.12 to 0.14% and now exhibit a near linear volume increase due to helium in-growth while showing possible surface effects on samples at 50 C and 65 C. The engineering stress of the accelerated alloy at 18 equivalent years increased significantly compared to at 4.5 equivalent years.

That National Ignition Facility (NIF) at Lawrence Livermore National Laboratory (LLNL) will be the world's largest and most energetic laser. It has thousands of optics and depends heavily on the quality and performance of these optics. Over the past several years, we have developed the NIF Optics Inspection Analysis System that automatically finds defects in a specific optic by analyzing images taken of that optic. This paper describes a new and complementary approach for the automatic detection of defects based on detecting the diffraction ring patterns in downstream optic images caused by defects in upstream optics. Our approach applies a robust pattern matching algorithm for images called Gradient Direction Matching (GDM). GDM compares the gradient directions (the direction of flow from dark to light) of pixels in a test image to those of a specified model and identifies regions in the test image whose gradient directions are most in line with those of the specified model. For finding rings, we use luminance disk models whose pixels have gradient directions all pointing toward the center of the disk. After GDM identifies potential rings locations, we rank these rings by how well they fit the theoretical diffraction ring pattern equation. We perform …

Experimental measurements using nanosecond time resolved embedded gauges and laser interferometric techniques, combined with Non-Equilibrium Zeldovich--von Neumann--Doring (NEZND) theory and Ignition and Growth reactive flow hydrodynamic modeling, have revealed the average pressure/particle velocity states attained in reaction zones of self-sustaining detonation waves in several solid and liquid explosives. The time durations of these reaction zone processes is discussed for explosives based on pentaerythritol tetranitrate (PETN), nitromethane, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), triaminitrinitrobenzene(TATB) and trinitrotoluene (TNT).

Chemistry and Materials Science Environmental Services (CES) is LLNL's on-site environmental analytical laboratory, analyzing approximately 2500 samples annually generally for waste characterization purposes. Due to the lack of process knowledge for analyzed samples, the waste produced by CES has traditionally been characterized on a ''worst-case'' basis as RCRA-hazardous mixed waste. By instituting rigorous ''up-front'' waste characterization, including segregation of acutely/extremely hazardous materials, utilizing regulatory exemptions, and developing a novel radiological characterization strategy, CES was able to receive approval for a certified LLW waste stream, adequately characterized for disposal at the Nevada Test Site. In the 10 months of operating history, CES has diverted 33% of its waste (by mass) from mixed to LLW. This will result in significant cost savings and reduction in waste re-handling/personnel exposure.

The U.S. LHC Accelerator Research Program (LARP), a collaboration between BNL, FNAL, LBNL, and SLAC, has among its major objectives the development of advanced magnet technology for an LHC luminosity upgrade. The LBNL Superconducting Magnet Group supports this program with a broad effort involving design studies, Nb{sub 3}Sn conductor development, mechanical models, and basic prototypes. This paper describes the development of a large aperture Nb{sub 3}Sn racetrack quadrupole magnet using four racetrack coils from the LBNL Subscale Magnet (SM) Program. The magnet provides a gradient of 95 T/m in a 110 mm bore, with a peak field in the conductor of 11.2 T. The coils are prestressed by a mechanical structure based on a pre-tensioned aluminum shell, and axially supported with aluminum rods. The mechanical behavior has been monitored with strain gauges and the magnetic field has been measured. Results of the test are reported and analyzed.

The formation and growth of sigma ({sigma}) phase in a 2205 duplex stainless steel is monitored during an 850 C isothermal heat treatment using an in situ synchrotron x-ray diffraction technique. At this temperature, {sigma} phase is first observed within approximately 40 seconds of the start of the isothermal heat treatment and grows rapidly over the course of the 3600 second heat treatment to a volume fraction of approximately 13%. A simultaneous increase in the austenite ({gamma}) volume fraction and a decrease in the ferrite ({delta}) volume fraction are observed. The {sigma} phase formed at this temperature is rapidly dissolved within approximately 200 seconds when the temperature is increased to 1000 C. Accompanying this rapid dissolution of the {sigma} phase, the {delta} and {gamma} volume fractions both approach the balanced (50/50) level observed in the as-received material.