Lanthanide Ionization Energies and the Sub-Shell Break. Part 2. The Third and Fourth Ionization Energies

By interpolating a 4fq6s → 4fq7s transition within the sequence f1 → f14 rather than between f0 and f14, revised third and fourth ionization energies of the lanthanides have been obtained. The revised values, together with the second ionization energies calculated in a previous paper, are used to calculate values of the standard enthalpies of formation of the gaseous tripositive ions, ΔfHƟ(M3+,g), and of the lattice and hydration enthalpies of some lanthanide compounds and ions in the trivalent and tetravalent states. The displacements of f0 values from nearly smooth f1 → f14 variations exceed 30 kJ mol-1 and indicate substantial subshell breaks

Valencies of the lanthanides

The valencies of the lanthanides vary more than was once thought. In addition to valencies associated with a half-full shell, there are valencies associated with a quarter- and three-quarter-full shell. This can be explained on the basis of Slater’s theory of many-electron atoms. The same theory explains the variation in complexing constants in the trivalent state (the “tetrad effect”). Valency in metallic and organometallic compounds is also discussed

Big Data, Digitization, and Social Change (Ubiquity Symposium)

The term “big data” is something of a misnomer. Every generation of computers since the 1950s has been confronted with problems where data was way too large for the memory and processing power available. This seemed like an inconvenience of the technology that would someday be resolved when the next generation of computers came along. So what is different about big data today? The revolution is happening at the convergence of two trends: the expansion of the internet into billions of computing devices, and the digitization of almost everything. The internet gives us access to vast amounts of data. Digitization creates digital representations for many things once thought to be beyond the reach of computing technology. The result is an explosion of innovation of network-based big data applications and the automation of cognitive tasks. This revolution is introducing what Brynjolfsson and McAfee call the “Second Machine Age.” This symposium will examine this revolution from a number of angles

Dark Matter Searches with Astroparticle Data

The existence of dark matter (DM) was first noticed by Zwicky in the 1930s, but its nature remains one of the great unsolved problems of physics. A variety of observations indicate that it is non-baryonic and non-relativistic. One of the preferred candidates for non-baryonic DM is a weakly interacting massive particle (WIMP) that in most models is stable. WIMP self-annihilation can produce cosmic rays, gamma rays, and other particles with signatures that may be detectable. Hints of anomalous cosmic-ray spectra found by recent experiments, such as PAMELA, have motivated interesting interpretations in terms of DM annihilation and/or decay. However, these signatures also have standard astrophysical interpretations, so additional evidence is needed in order to make a case for detection of DM annihilation or decay. Searches by the Fermi Large Area Telescope for gamma-ray signals from clumps, nearby dwarf spheroidal galaxies, and galaxy clusters have also been performed, along with measurements of the diffuse Galactic and extragalactic gamma-ray emission. In addition, imaging atmospheric Cherenkov telescopes like HESS, MAGIC, and VERITAS have reported on searches for gamma-ray emission from dwarf galaxies. In this review, we examine the status of searches for particle DM by these instruments and discuss the interpretations and resulting DM limits.Comment: Solicited review article to appear in Annual Reviews of Astronomy and Astrophysics. 52 pages, 10 figures (higher resolution figures will appear in the journal article

Eurasian watermilfoil biomass associated with insect herbivores in New York

A study of aquatic plant biomass within Cayuga Lake, New York spans twelve years from 1987-1998. The exotic Eurasian watermilfoil ( Myriophyllum spicatum L.) decreased in the northwest end of the lake from 55% of the total biomass in 1987 to 0.4% in 1998 and within the southwest end from 50% in 1987 to 11% in 1998. Concurrent with the watermilfoil decline was the resurgence of native species of submersed macrophytes. During this time we recorded for the first time in Cayuga Lake two herbivorous insect species: the aquatic moth Acentria ephemerella , first observed in 1991, and the aquatic weevil Euhrychiopsis lecontei , first found in 1996 . Densities of Acentria in southwest Cayuga Lake averaged 1.04 individuals per apical meristem of Eurasian watermilfoil for the three-year period 1996-1998. These same meristems had Euhrychiopsis densities on average of only 0.02 individuals per apical meristem over the same three-year period. A comparison of herbivore densities and lake sizes from five lakes in 1997 shows that Acentria densities correlate positively with lake surface area and mean depth, while Euhrychiopsis densities correlate negatively with lake surface area and mean depth. In these five lakes, Acentria densities correlate negatively with percent composition and dry mass of watermilfoil. However, Euhrychiopsis densities correlate positively with percent composition and dry mass of watermilfoil. Finally, Acentria densities correlate negatively with Euhrychiopsis densities suggesting interspecific competition

Characterizing New Channels of Communication: A Case Study of Municipal 311 Requests in Edmonton, Canada

City governments around the world are developing and expanding how they connect to citizens. Technologies play an important role in making this connection, and one frequent way that cities connect with citizens is through 311-style request systems. 311 is a non-emergency municipal notification system that uses telephone, email, web forms, and increasingly, mobile applications to allow citizens to notify government of infrastructure issues and make requests for municipal services. In many ways, this process of citizen contribution mirrors the provision of volunteered geographic information, that is spatially-referenced user generated content. This research presents a case study of the city of Edmonton, Canada, an early adopter of multi-channel 311 service request systems, including telephone, email, web form, and mobile app 311 request channels. Three methods of analysis are used to characterize and compare these different channels over three years of request data; a comparison of relative request share for each channel, a spatial hot spot analysis, and regression models to compare channel usage with sociodemographic variables. The results of this study indicate a shift in channel usage from traditional to Internet-enabled, that this shift is mirrored in the hotspots of request activity, and that specific digital inequalities exist that reinforce this distinction between traditional and Internet-enabled reporting channels

High Reynolds number tests of a Douglas DLBA 032 airfoil in the Langley 0.3-meter transonic cryogenic tunnel

A wind-tunnel investigation of a Douglas advanced-technology airfoil was conducted in the Langley 0.3-Meter Transonic Cryogenic Tunnel (0.3-m TCT). The temperature was varied from 227 K (409 R) to 100 K (180 R) at pressures ranging from about 159 kPa (1.57 atm) to about 514 kPa (5.07 atm). Mach number was varied from 0.50 to 0.78. These variables provided a Reynolds number range (based on airfoil chord) from 6.0 to 30.0 x 10 to the 6th power. This investigation was specifically designed to: (1) test a Douglas airfoil from moderately low to flight-equivalent Reynolds numbers, and (2) evaluate sidewall-boundary-layer effects on transonic airfoil performance characteristics by a systematic variation of Mach number, Reynolds number, and sidewall-boundary-layer removal. Data are included which demonstrate the effects of fixing transition, Mach number, Reynolds number, and sidewall-boundary-layer removal on the aerodynamic characteristics of the airfoil. Also included are remarks on model design and model structural integrity

The Geoweb for community-based organizations: Tool development, implementation, and sustainability in an era of Google Maps

Recent advances in web-based geospatial tools (the Geoweb) show promise as low-cost and easy-to-use methods to support citizen participation. This research presents two case studies of Geoweb implementation set in community-based organizations in rural Quebec, Canada. When comparing the development and sustainability of each Geoweb tool, the implementation time frame plays a key role. Two implementation time frames are defined; a discrete, or ‘one-off’ time frame associated with lower resource requirements, and a continuous, or ongoing time frame, that has a higher total resource cost, but can fulfill a different set of goals than a discrete implementation

Simple and inexpensive perturbative correction schemes for antisymmetric products of nonorthogonal geminals

A new multireference perturbation approach has been developed for the recently proposed AP1roG scheme, a computationally facile parametrization of an antisymmetric product of nonorthogonal geminals. This perturbation theory of second-order closely follows the biorthogonal treatment from multiconfiguration perturbation theory as introduced by Surjan et al., but makes use of the additional feature of AP1roG that the expansion coefficients within the space of closed-shell determinants are essentially correct already, which further increases the predictive power of the method. Building upon the ability of AP1roG to model static correlation, the perturbation correction accounts for dynamical electron correlation, leading to absolute energies close to full configuration interaction results. Potential surfaces for multiple bond dissociation in H2O and N-2 are predicted with high accuracy up to bond breaking. The computational cost of the method is the same as that of conventional single-reference MP2