Gas Phase Hydrolysis and Oxo-Exchange of Actinide Dioxide Cations: Elucidating Intrinsic Chemistry from Protactinium to Einsteinium.

Gas-phase bimolecular reactions of metal cations with water provide insights into intrinsic characteristics of hydrolysis. For the actinide dioxide cations, actinyl(V) AnO2 + , melding of experiment and computation provides insights into trends for hydrolysis, as well as for oxo-exchange between actinyls and water that proceeds by a hydrolysis pathway. Here this line of inquiry is further extended into the actinide series with CCSD(T) computations of potential energy surfaces, for the reaction pathway for oxo-exchange through hydrolysis of nine actinyl(V) ions, from PaO2 + to EsO2 + . The computed surfaces are in accord with previous experimental results for oxo-exchange, and furthermore predict spontaneous exchange for CmO2 + , BkO2 + , CfO2 + and EsO2 + , but not for AmO2 + . Natural Bond Order analysis of the species involved in both hydrolysis and oxo-exchange reveals an inverse correlation between the barrier to hydrolysis and the charge on the actinide centre, q(An). Based on this correlation, it can be concluded that hydrolysis, and related phenomena such as oxo-exchange, become less favourable as the charge on the metal centre decreases. The new results provide a straightforward rationalization of trends across a wide swathe of the actinide series

Activation of Water by Pentavalent Actinide Dioxide Cations: Characteristic Curium Revealed by a Reactivity Turn after Americium.

Swapping of an oxygen atom of water with that of a pentavalent actinide dioxide cation, AnO2+ also called an "actinyl", requires activation of an An-O bond. It was previously found that such oxo exchange in the gas phase occurs for the first two actinyls, PaO2+ and UO2+, but not the next two, NpO2+ and PuO2+. The An-O bond dissociation energies (BDEs) decrease from PaO2+ to PuO2+, such that the observation of a parallel decrease in the An-O bond reactivity is intriguing. To elucidate oxo exchange, we here extend experimental studies to AmO2+, americyl(V), and CmO2+, curyl(V), which were produced in remarkable abundance by electrospray ionization of Am3+ and Cm3+ solutions. Like other AnO2+, americyl(V) and curyl(V) adsorb up to four H2O molecules to form tetrahydrates AnO2(H2O)4+ with the actinide hexacoordinated by oxygen atoms. It was found that AmO2+ does not oxo-exchange, whereas CmO2+ does, establishing a "turn" to increasing the reactivity from americyl to curyl, which validates computational predictions. Because oxo exchange occurs via conversion of an actinyl(V) hydrate, AnO2(H2O)+, to an actinide(V) hydroxide, AnO(OH)2+, it reflects the propensity for actinyl(V) hydrolysis: PaO2+ hydrolyzes and oxo-exchanges most easily, despite the fact that it has the highest BDE of all AnO2+. A reexamination of the computational results for actinyl(V) oxo exchange reveals distinctive properties and chemistry of curyl(V) species, particularly CmO(OH)2+

Interferometric weak value deflections: quantum and classical treatments

We derive the weak value deflection given in a paper by Dixon et al. (Phys. Rev. Lett. 102, 173601 (2009)) both quantum mechanically and classically. This paper is meant to cover some of the mathematical details omitted in that paper owing to space constraints

Characterising regional landslide initiation thresholds in Scotland, UK using NIMROD c-band precipitation radar and the BGS National Landslide Database

Characterising regional landslide initiation thresholds in Scotland, UK using NIMROD c-band precipitation radar and the BGS National Landslide Databas

Indirect economic impact of landslide hazards by disruption to national road transportation networks; Scotland, United Kingdom

Indirect economic impact of landslide hazards by disruption to national road transportation networks; Scotland, United Kingdo

Late Cretaceous and Paleogene tectonic evolution of the North Pacific Ocean

The Late Cretaceous history of the northern Pacific Ocean has not been adequately deciphered, largely because a major plate reorganization occurred during the Cretaceous magnetic quiet interval. Using primary data to reconstruct plate motions from fracture zone trends and Late Cretaceous seafloor spreading magnetic anomalies allows formulation of a reasonable sequence of events that accounts for all the geologic features of that region, especially the Emperor and Chinook troughs. The primary event in our reconstruction is the subduction of the old northwest Pacific triple junction. New relative plate motions imposed by formation of convergent boundaries along both the northern Pacific and Farallon plates caused the Farallon plate to crack. This subdivision occurred 82 m.y. ago and resulted in the formation of the Kula and Chinook plates. The Chinook plate was bounded on the north by the Chinook-Kula ridge, the western arm of the Great Magnetic Bight, on the west by the southern Emperor trough, a slowly spreading rift valley, on the south by the Mendocino transform, and on the east by the Chinook-Farallon ridge. The northern Emperor trough formed the initial western boundary of the Kula plate. From 82 m.y. ago to 50 m.y. ago this configuration was stable: the Chinook plate expanded, the Chinook-Kula ridge migrated north, and the Kula plate was subducted. With the subduction of this ridge, the Chinook plate adhered to the Pacific plate and the Pacific-Farallon ridge became the north-south-trending feature reflected by anomalies 22 and younger.This reconstruction obviates the awkward Late Cretaceous shifting of triple junctions found in other proposed histories and provides reasonable explanations for the several structural features of the region. To achieve closure of vector triangles representing the relative Late Cretaceous plate motions some extension must occur, presumably across the eastern Mendocino fracture zone, between the northern and southern portions of the Farallon plate. These two plates apparently were independent units between 105 and 50 m.y. ago; the initiation and cessation of rapid North Farallon-North American convergence 82 and 50 m.y. ago may have determined the nature and duration of the Laramide orogeny.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/25097/1/0000529.pd

Next-to-Leading order Higgs + 2 jet production via gluon fusion

We present phenomenological results for the production of a Higgs boson in association with two jets at the LHC. The calculation is performed in the limit of large top mass and is accurate to next-to-leading order in the strong coupling, i.e. ${\cal O}(\alpha_s^6)$Comment: 13 pages, 6 figures; v2: references added, modified acknowledgments, final version as published in JHE

Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium.

Actinyl chemistry is extended beyond Cm to BkO2+ and CfO2+ through transfer of an O atom from NO2 to BkO+ or CfO+ , establishing a surprisingly high lower limit of 73 kcal mol-1 for the dissociation energies, D[O-(BkO+ )] and D[O-(CfO+ )]. CCSD(T) computations are in accord with the observed reactions, and characterize the newly observed dioxide ions as linear pentavalent actinyls; these being the first Bk and Cf species with oxidation states above IV. Computations of actinide dioxide cations AnO2+ for An=Pa to Lr reveal an unexpected minimum for D[O-(CmO+ )]. For CmO2+ , and AnO2+ beyond EsO2+ , the most stable structure has side-on bonded η2 -(O2 ), as AnIII peroxides for An=Cm and Lr, and as AnII superoxides for An=Fm, Md, and No. It is predicted that the most stable structure of EsO2+ is linear [O=EsV =O]+ , einsteinyl, and that FmO2+ and MdO2+ , like CmO2+ , also have actinyl(V) structures as local energy minima. The results expand actinide oxidation state chemistry, the realm of the distinctive actinyl moiety, and the non-periodic character towards the end of the periodic table

Interferometric Weak Value Deflections: Quantum and Classical Treatments

We derive the weak value deflection given in an article by Dixon et al. [P. B. Dixon et al. Phys. Rev. Lett. 102 173601 (2009)] both quantum mechanically and classically, including diffraction effects. This article is meant to cover some of the mathematical details omitted in that article owing to space constraints

HYDRAULIC AND PHYSICAL PROPERTIES OF SALTSTONE GROUTS AND VAULT CONCRETES

The Saltstone Disposal Facility (SDF), located in the Z-Area of the Savannah River Site (SRS), is used for the disposal of low-level radioactive salt solution. The SDF currently contains two vaults: Vault 1 (6 cells) and Vault 4 (12 cells). Additional disposal cells are currently in the design phase. The individual cells of the saltstone facility are filled with saltstone. Saltstone is produced by mixing the low-level radioactive salt solution, with blast furnace slag, fly ash, and cement (dry premix) to form a dense, micro-porous, monolithic, low-level radioactive waste form. The saltstone is pumped into the disposal cells where it subsequently solidifies. Significant effort has been undertaken to accurately model the movement of water and contaminants through the facility. Key to this effort is an accurate understanding of the hydraulic and physical properties of the solidified saltstone. To date, limited testing has been conducted to characterize the saltstone. The primary focus of this task was to estimate the hydraulic and physical properties of three types of saltstone and two vault concretes. The saltstone formulations included saltstone premix batched with (1) Deliquification, Dissolution, and Adjustment (DDA) salt simulant (w/pm 0.60), (2) Actinide Removal Process (ARP)/Modular Caustic Side Solvent Extraction Unit (MCU) salt simulant (w/pm 0.60), and (3) Salt Waste Processing Facility (SWPF) salt simulant (w/pm 0.60). The vault concrete formulations tested included the Vault 1/4 concrete and two variations of the Vault 2 concrete (Mix 1 and Mix 2). Wet properties measured for the saltstone formulations included yield stress, plastic viscosity, wet unit weight, bleed water volume, gel time, set time, and heat of hydration. Hydraulic and physical properties measured on the cured saltstone and concrete samples included saturated hydraulic conductivity, moisture retention, compressive strength, porosity, particle density, and dry bulk density. These properties were determined following a minimum 28 day curing period. Additional testing of the three saltstone formulations was conducted following a minimum 90 day curing period. The compressive strength of each saltstone and concrete material was measured at approximately 14, 28, 56, and 90 days. Recommended hydraulic property values for each saltstone grout and the vault concretes are provided. The hydraulic properties provided for each material include the saturated hydraulic conductivity, dry bulk density, particle density, and porosity. In addition, water retention data are presented for each material along with the van Genuchten transport parameters as determined using the RETC code