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.

The present paper presents the {sup 36}Cl measurement effort in the US. A large number of {sup 36}Cl measurements have been made in both granite and concrete samples obtained from various locations and distances in Hiroshima and Nagasaki. These measurements employed accelerator mass spectrometry (AMS) to quantify the number of atoms of {sup 36}Cl per atom of total Cl in the sample. Results from these measurements are presented here and discussed in the context of the DS02 dosimetry reevaluation effort for Hiroshima and Nagasaki atomic-bomb survivors. The production of {sup 36}Cl by bomb neutrons in mineral samples from Hiroshima and Nagasaki was primarily via the reaction {sup 35}Cl(n,{gamma}){sup 36}Cl. This reaction has a substantial thermal neutron cross-section (43.6 b at 0.025 eV) and the product has a long half-life (301,000 y). hence, it is well suited for neutron-activation detection in Hiroshima and Nagasaki using AMS more than 50 years after the bombings. A less important reaction for bomb neutrons, {sup 39}K(n,{alpha}){sup 36}Cl, typically produces less than 10% of the {sup 36}Cl in mineral samples such as granite and concrete, which contain {approx} 2% potassium. In 1988, only a year after the publication of the DS86 final report (Roesch 1987), it …

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Atmospheric chemistry and aerosols have several important roles in climate change. They affect the Earth's radiative balance directly: cooling the earth by scattering sunlight (aerosols) and warming the Earth by trapping the Earth's thermal radiation (methane, ozone, nitrous oxide, and CFCs are greenhouse gases). Atmospheric chemistry and aerosols also impact many other parts of the climate system: modifying cloud properties (aerosols can be cloud condensation nuclei), fertilizing the biosphere (nitrogen species and soil dust), and damaging the biosphere (acid rain and ozone damage). In order to understand and quantify the effects of atmospheric chemistry and aerosols on the climate and the biosphere in the future, it is necessary to incorporate atmospheric chemistry and aerosols into state-of-the-art climate system models. We have taken several important strides down that path. Working with the latest NCAR Community Climate System Model (CCSM), we have incorporated a state-of-the-art atmospheric chemistry model to simulate tropospheric ozone. Ozone is not just a greenhouse gas, it damages biological systems including lungs, tires, and crops. Ozone chemistry is also central to the oxidizing power of the atmosphere, which destroys a lot of pollutants in the atmosphere (which is a good thing). We have also implemented a fast chemical mechanism …

In the spring of 2002, Argonne National Laboratory founded the Laboratory Computing Resource Center, and in April 2003 LCRC began full operations with Argonne's first teraflops computing cluster. The LCRC's driving mission is to enable and promote computational science and engineering across the Laboratory, primarily by operating computing facilities and supporting application use and development. This report describes the scientific activities, computing facilities, and usage in the first eighteen months of LCRC operation. In this short time LCRC has had broad impact on programs across the Laboratory. The LCRC computing facility, Jazz, is available to the entire Laboratory community. In addition, the LCRC staff provides training in high-performance computing and guidance on application usage, code porting, and algorithm development. All Argonne personnel and collaborators are encouraged to take advantage of this computing resource and to provide input into the vision and plans for computing and computational analysis at Argonne. Steering for LCRC comes from the Computational Science Advisory Committee, composed of computing experts from many Laboratory divisions. The CSAC Allocations Committee makes decisions on individual project allocations for Jazz.

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.

We have attempted to fabricate some 0.5 mm diameter D{sub 2}-gas-filled Be shells by coating gas-filled PVA-coated GDP mandrels with Cu-doped Be. We find that during the coating all (or most) of the gas leaks out. This is likely due to either small cracks or holes in the coating that are formed at the earliest points and are maintained during the thickness build-up of the coating, and/or to some level of intrinsic porosity in the coating. This memo documents our efforts.

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.

This chapter describes ex situ bioremediation of the petroleum portion of radiologically co-contaminated soils using microorganisms isolated from a waste site and innovative bioreactor technology. Microorganisms first isolated and screened in the laboratory for bioremediation of petroleum were eventually used to treat soils in a bioreactor. The bioreactor treated soils contaminated with over 20,000 mg/kg total petroleum hydrocarbon and reduced the levels to less than 100 mg/kg in 22 months. After treatment, the soils were permanently disposed as low-level radiological waste. The petroleum and radiologically contaminated soil (PRCS) bioreactor operated using bioventing to control the supply of oxygen (air) to the soil being treated. The system treated 3.67 tons of PCRS amended with weathered compost, ammonium nitrate, fertilizer, and water. In addition, a consortium of microbes (patent pending) isolated at the Savannah River National Laboratory from a petroleum-contaminated site was added to the PRCS system. During operation, degradation of petroleum waste was accounted for through monitoring of carbon dioxide levels in the system effluent. The project demonstrated that co-contaminated soils could be successfully treated through bioventing and bioaugmentation to remove petroleum contamination to levels below 100 mg/kg while protecting workers and the environment from radiological contamination.

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.

Research results are the areas of catalyst precursor synthesis, catalyst fluxionality, catalyst stability, polymerization of {alpha}-olefins as well as the chemistry of Group IV and Group V metal centers with aryloxide and arylsulfide ligands.

The purposes of this analysis are: (1) Categorize (as Category 1, Category 2, or Beyond Category 2) internal event sequences that may occur before permanent closure of the repository at Yucca Mountain. (2) Categorize external event sequences that may occur before permanent closure of the repository at Yucca Mountain. This includes examining DBGM-1 seismic classifications and upgrading to DBGM-2, if appropriate, to ensure Beyond Category 2 categorization. (3) State the design and operational requirements that are invoked to make the categorization assignments valid. (4) Indicate the amount of material put at risk by Category 1 and Category 2 event sequences. (5) Estimate frequencies of Category 1 event sequences at the maximum capacity and receipt rate of the repository. (6) Distinguish occurrences associated with normal operations from event sequences. It is beyond the scope of the analysis to propose design requirements that may be required to control radiological exposure associated with normal operations. (7) Provide a convenient compilation of the results of the analysis in tabular form. The results of this analysis are used as inputs to the consequence analyses in an iterative design process that is depicted in Figure 1. Categorization of event sequences for permanent retrieval of waste from …

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.

Recently developed nuclear many-body techniques provide novel results when applied to constituent quark models and to light-front scalar field theory. We show how spontaneous symmetry breaking arises and is consistent with a coherent state ansatz in a variational treatment. The kink and the kink-antikink topological features are identified and the onset of symmetry restoration is demonstrated.

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.