Rhodium Pyrazolate Complexes as Potential CVD Precursors

Reaction of 3,5-(CF3)(2)PzLi with [Rh(mu-Cl)(eta(2)-C2H4)(2)](2) or [Rh(mu-Cl)(PMe3)(2)](2) in Et2O gave the dinuclear complexes [Rh(eta(2)-C2H4)(2)(mu-3,5-(CF3)(2)-Pz)](2) (1) and [Rh-2(mu-Cl)(mu-3,5-(CF3)(2)-Pz) (PMe3)(4)] (2) respectively (3,5-(CF3)(2)Pz = bis-trifluoromethyl pyrazolate). Reaction of PMe3 with [Rh(COD)(mu-3,5-(CF3)(2)-Pz)](2) in toluene gave [Rh(3,5-(CF3)(2)-Pz)(PMe3)(3)] (3). Reaction of 1 and 3 in toluene (1 : 4) gave moderate yields of the dinuclear complex [Rh(PMe3)(2)(mu-3,5-(CF3)(2)-Pz)](2) (4). Reaction of 3,5-(CF3)(2)PzLi with [Rh(PMe3)(4)]Cl in Et2O gave the ionic complex [Rh(PMe3)(4)][3,5-(CF3)(2)-Pz] (5). Two of the complexes, 1 and 3, were studied for use as CVD precursors. Polycrystalline thin films of rhodium (fcc-Rh) and metastable-amorphous films of rhodium phosphide (Rh2P) were grown from 1 and 3 respectively at 170 and 130 degrees C, 0.3 mmHg in a hot wall reactor using Ar as the carrier gas (5 cc min(-1)). Thin films of amorphous rhodium and rhodium phosphide (Rh2P) were grown from 1 and 3 at 170 and 130 degrees C respectively at 0.3 mmHg in a hot wall reactor using H-2 as the carrier gas (7 cc min(-1)).Welch Foundation F-816Petroleum Research Fund 47014-ACSNSF 0741973Chemistr

New Dimensions for Wound Strings: The Modular Transformation of Geometry to Topology

We show, using a theorem of Milnor and Margulis, that string theory on compact negatively curved spaces grows new effective dimensions as the space shrinks, generalizing and contextualizing the results in hep-th/0510044. Milnor's theorem relates negative sectional curvature on a compact Riemannian manifold to exponential growth of its fundamental group, which translates in string theory to a higher effective central charge arising from winding strings. This exponential density of winding modes is related by modular invariance to the infrared small perturbation spectrum. Using self-consistent approximations valid at large radius, we analyze this correspondence explicitly in a broad set of time-dependent solutions, finding precise agreement between the effective central charge and the corresponding infrared small perturbation spectrum. This indicates a basic relation between geometry, topology, and dimensionality in string theory.Comment: 28 pages, harvmac big. v2: references and KITP preprint number added, minor change

Modelling the effects of climate on long-term patterns of dissolved organic carbon concentrations in the surface waters of a boreal catchment

International audienceDissolved organic carbon concentrations ([DOC]) in surface waters are increasing in many regions of Europe and North America. These increases are likely driven by a combination of changing climate, recovery from acidification and change in severity of winter storms in coastal areas. INCA-C, a process-based model of climate effects on surface water [DOC], was used to explore the mechanisms by which changing climate controls seasonal to inter-annual patterns of [DOC] in the lake and outflow stream of a small Finnish catchment between 1990 and 2003. Both production in the catchment and mineralization in the lake controlled [DOC] in the lake. Concentrations in the catchment outflow were controlled by rates of DOC production in the surrounding organic soils. The INCA-C simulation results were compared to those obtained using artificial neural networks (ANN). In general, "black box" ANN models provide better fits to observed data but process-based models can identify the mechanism responsible for the observed pattern. A statistically significant increase was observed in both INCA-C modelled and measured annual average [DOC] in the lake. This suggests that some of the observed increase in surface water [DOC] is caused by climate-related processes operating in the lake and catchment. However, a full understanding of surface water [DOC] dynamics can only come from catchment-scale process-based models linking the effects of changing climate and deposition on aquatic and terrestrial environments

Ratcheting Heat Flux against a Thermal Bias

Merely rocking the temperature in one heat bath can direct a steady heat flux from cold to hot against a non-zero thermal bias in stylized nonlinear lattice junctions that are sandwiched between two heat baths. Likewise, for an average zero-temperature difference between the two contacts a net, ratchet-like heat flux emerges. Computer simulations show that this very heat flux can be controlled and reversed by suitably tailoring the frequency ($\lesssim$ 100 MHz) of the alternating temperature field.Comment: 5 pages, 6 figure

Effect of water-wall interaction potential on the properties of nanoconfined water

Much of the understanding of bulk liquids has progressed through study of the limiting case in which molecules interact via purely repulsive forces, such as a hard-core potential. In the same spirit, we report progress on the understanding of confined water by examining the behavior of water-like molecules interacting with planar walls via purely repulsive forces and compare our results with those obtained for Lennard-Jones (LJ) interactions between the molecules and the walls. Specifically, we perform molecular dynamics simulations of 512 water-like molecules which are confined between two smooth planar walls that are separated by 1.1 nm. At this separation, there are either two or three molecular layers of water, depending on density. We study two different forms of repulsive confinements, when the interaction potential between water-wall is (i) $1/r^9$ and (ii) WCA-like repulsive potential. We find that the thermodynamic, dynamic and structural properties of the liquid in purely repulsive confinements qualitatively match those for a system with a pure LJ attraction to the wall. In previous studies that include attractions, freezing into monolayer or trilayer ice was seen for this wall separation. Using the same separation as these previous studies, we find that the crystal state is not stable with $1/r^9$ repulsive walls but is stable with WCA-like repulsive confinement. However, by carefully adjusting the separation of the plates with $1/r^9$ repulsive interactions so that the effective space available to the molecules is the same as that for LJ confinement, we find that the same crystal phases are stable. This result emphasizes the importance of comparing systems only using the same effective confinement, which may differ from the geometric separation of the confining surfaces.Comment: 20 pages, 10 figure

Identification of capacity development indicators for faculty development programs: A nominal group technique study.

BackgroundAlthough there have been many research studies of the effectiveness of faculty development in health profession education, the contribution of these programs to organizational development through capacity development has not been studied. Further understanding of capacity development requires appropriate indicators and no previous indicators for faculty development of health profession educators were identified. The aim of the study was to identify indicators of capacity development in the context of faculty development programs at Tehran University of medical sciences (TUMS).MethodsA nominal group technique session was conducted with key informants from faculty development program providers to generate and prioritize a list of capacity development indicators.ResultsA list of 26 indicators was generated and five categories were identified: Development and innovation in teaching and learning process, Development and innovation in communication and collaboration at different levels, Development and sustaining faculty development programs, Development of educational leadership and management, Development in scholarship.ConclusionsCapacity development for faculty development interventions of health profession educators is a process of engagement within a wider system, including individual and collective action, and involves the socialization of the teachers into suitable roles through professional identity development and participation within the wider system

Thermodynamic and structural aspects of the potential energy surface of simulated water

Relations between the thermodynamics and dynamics of supercooled liquids approaching a glass transition have been proposed over many years. The potential energy surface of model liquids has been increasingly studied since it provides a connection between the configurational component of the partition function on one hand, and the system dynamics on the other. This connection is most obvious at low temperatures, where the motion of the system can be partitioned into vibrations within a basin of attraction and infrequent inter-basin transitions. In this work, we present a description of the potential energy surface properties of supercooled liquid water. The dynamics of this model has been studied in great details in the last years. Specifically, we locate the minima sampled by the liquid by ``quenches'' from equilibrium configurations generated via molecular dynamics simulations. We calculate the temperature and density dependence of the basin energy, degeneracy, and shape. The temperature dependence of the energy of the minima is qualitatively similar to simple liquids, but has anomalous density dependence. The unusual density dependence is also reflected in the configurational entropy, the thermodynamic measure of degeneracy. Finally, we study the structure of simulated water at the minima, which provides insight on the progressive tetrahedral ordering of the liquid on cooling

GPs are from Mars, Administrators are from Venus: The Role of Misaligned Occupational Dispositions in Inhibiting Mandated Role Change

Research on mandated occupational role change focuses on jurisdictional conflict to explain change failure. Our study of the English National Health Service highlights the role of occupational dispositions in shaping how mandated role change is implemented by members of multiple occupational groups. We find that tension stemming from misaligned dispositions may emerge as members of different occupations interact during their role change implementation efforts. Depending on dispositional responses to tension, change may fail as members of the different occupations avoid interactions. This suggests that effective role change can be elusive even in the initial absence of conflicting occupational interests

Movements of bocaccio (Sebastes paucispinis) and greenspotted (S. chlorostictus) rockfishes in a Monterey submarine canyon: implications for the design of marine reserves

In August and September of 1997 and 1998, we used SCUBA techniques to surgically implant Vemco V16 series acoustic transmitters in 6 greenspotted rockfish (Sebastes chlorostictus) and 16 bocaccio (S. paucispinis) on the flank of Soquel Canyon in Monterey Bay, California. Fish were captured at depths of 100–200 m and reeled up to a depth of approximately 20 m, where a team of SCUBA divers anesthetized and surgically implanted acoustic transmitters in them. Tagged fish were released on the seafloor at the location of catch. An array of recording receivers on the seafloor enabled the tracking of horizontal and vertical fish movements for a three-month period. Greenspotted rockfish tagged in 1997 exhibited almost no vertical movement and showed limited horizontal movement. Two of these tagged fish spent more than 90% of the time in a 0.58-km2 area. Three other tagged greenspotted rockfish spent more than 60% of the time in a 1.6-km2 area but displayed frequent horizontal movements of at least 3 km. Bocaccio exhibited somewhat greater movements. Of the 16 bocaccio tagged in 1998, 10 spent less than 10% of the time in the approximately 12-km2 study area. One fish stayed in the study area for about 50% of the study time. Signals from the remaining 5 fish were recorded in the study area the entire time. Bocaccio frequently moved vertically 10–20 m and occasionally displayed vertical movements of 100 m or greater