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

Interpenetration as a Mechanism for Liquid-Liquid Phase Transitions

We study simple lattice systems to demonstrate the influence of interpenetrating bond networks on phase behavior. We promote interpenetration by using a Hamiltonian with a weakly repulsive interaction with nearest neighbors and an attractive interaction with second-nearest neighbors. In this way, bond networks will form between second-nearest neighbors, allowing for two (locally) distinct networks to form. We obtain the phase behavior from analytic solution in the mean-field approximation and exact solution on the Bethe lattice. We compare these results with exact numerical results for the phase behavior from grand canonical Monte Carlo simulations on square, cubic, and tetrahedral lattices. All results show that these simple systems exhibit rich phase diagrams with two fluid-fluid critical points and three thermodynamically distinct phases. We also consider including third-nearest-neighbor interactions, which give rise to a phase diagram with four critical points and five thermodynamically distinct phases. Thus the interpenetration mechanism provides a simple route to generate multiple liquid phases in single-component systems, such as hypothesized in water and observed in several model and experimental systems. Additionally, interpenetration of many such networks appears plausible in a recently considered material made from nanoparticles functionalized by single strands of DNA.Comment: 12 pages, 9 figures, submitted to Phys. Rev.

Intercomparison of standard resolution and high resolution TOVS soundings with radiosonde, lidar, and surface temperature/humidity data

One objective of the FIRE Cirrus IFO is to characterize relationships between cloud properties inferred from satellite observations at various scales to those obtained directly or inferred from very high resolution measurements. Satellite derived NOAA-9 high and standard resolution Tiros Operational Vertical Sounder (TOVS) soundings are compared with directly measured lidar, surface temperature, humidity, and vertical radiosonde profiles associated with the Ft. McCoy site. The results of this intercomparison should be useful in planning future cloud experiments

Electronic heat current rectification in hybrid superconducting devices

In this work, we review and expand recent theoretical proposals for the realization of electronic thermal diodes based on tunnel-junctions of normal metal and superconducting thin films. Starting from the basic rectifying properties of a single hybrid tunnel junction, we will show how the rectification efficiency can be largely increased by combining multiple junctions in an asymmetric chain of tunnel-coupled islands. We propose three different designs, analyzing their performance and their potential advantages. Besides being relevant from a fundamental physics point of view, this kind of devices might find important technological application as fundamental building blocks in solid-state thermal nanocircuits and in general-purpose cryogenic electronic applications requiring energy management.Comment: 9 pages, 5 color figure

In situ observations of ClO in the Antarctic: Evidence for chlorine catalyzed destruction of ozone

Results from a series of 12 ER-2 aircraft flights into the Antarctic polar vortex are summarized. These in situ data define the spatial and temporal distribution of ClO as the aircraft flew at an altitude of approx. 18 km from Punta Arenas (54 deg S latitude) to the base of the Palmer Peninsula (72 deg S latitude), executed a rapid descent to approx. 13 km, turned north and climbed bach to approximately 18 km, returning to Punta Arenas. A general pattern in the ClO distribution is reported: mixing ratios of approximately 10 ppt are found at altitude in the vicinity of 55 deg S increasing to 50 ppt at 60 degrees S. In the vicinity of 65 deg S latitude a steep gradient in the ClO mixing ratio is observed. At a fixed potential temperature, the ClO mixing ratio through this sharp transition increases by an order of magnitude within a very few degrees of latitude, thus defining the edge of the chemical containment vessel. From the edge of that containment vessel to the southern extension of the flights, 72 deg S, a dome of slowly increasing ClO best describes the distribution. Conclusion are drawn from the data

Potential Energy Landscape of the Apparent First-Order Phase Transition between Low-Density and High-Density Amorphous Ice

The potential energy landscape (PEL) formalism is a valuable approach within statistical mechanics for describing supercooled liquids and glasses. Here we use the PEL formalism and computer simulations to study the pressure-induced transformations between low-density amorphous ice (LDA) and high-density amorphous ice (HDA) at different temperatures. We employ the ST2 water model for which the LDA-HDA transformations are remarkably sharp, similar to what is observed in experiments, and reminiscent of a first-order phase transition. Our results are consistent with the view that LDA and HDA configurations are associated with two distinct regions (megabasins) of the PEL that are separated by a potential energy barrier. At higher temperature, we find that low-density liquid (LDL) configurations are located in the same megabasin as LDA, and that high-density liquid (HDL) configurations are located in the same megabasin as HDA. We show that the pressure-induced LDL-HDL and LDA-HDA transformations occur along paths that interconnect these two megabasins, but that the path followed by the liquid is different than the path followed by the amorphous solid. At higher pressure, we also study the liquid-to-ice-VII first-order phase transition, and find that the behavior of the PEL properties across this transition are qualitatively similar to the changes found during the LDA-HDA transformation. This similarity supports the interpretation that the LDA-HDA transformation is a first-order-like phase transition between out-of-equilibrium states.Comment: 29 pages, 8 figure

TALON - The Telescope Alert Operation Network System: Intelligent Linking of Distributed Autonomous Robotic Telescopes

The internet has brought about great change in the astronomical community, but this interconnectivity is just starting to be exploited for use in instrumentation. Utilizing the internet for communicating between distributed astronomical systems is still in its infancy, but it already shows great potential. Here we present an example of a distributed network of telescopes that performs more efficiently in synchronous operation than as individual instruments. RAPid Telescopes for Optical Response (RAPTOR) is a system of telescopes at LANL that has intelligent intercommunication, combined with wide-field optics, temporal monitoring software, and deep-field follow-up capability all working in closed-loop real-time operation. The Telescope ALert Operations Network (TALON) is a network server that allows intercommunication of alert triggers from external and internal resources and controls the distribution of these to each of the telescopes on the network. TALON is designed to grow, allowing any number of telescopes to be linked together and communicate. Coupled with an intelligent alert client at each telescope, it can analyze and respond to each distributed TALON alert based on the telescopes needs and schedule.Comment: Presentation at SPIE 2004, Glasgow, Scotland (UK