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Transient cavities and the excess chemical potentials of hard-spheroid solutes in dipolar hard sphere solvents

Monte Carlo computer simulations are used to study transient cavities and the solvation of hard-spheroid solutes in dipolar hard sphere solvents. The probability distribution of spheroidal cavities in the solvent is shown to be well described by a Gaussian function, and the variations of fit parameters with cavity elongation and solvent properties are analyzed. The excess chemical potentials of hard-spheroid solutes with aspect ratios $x$ in the range $1/5 \leq x \leq 5$, and with volumes between one and twenty times that of a solvent molecule, are presented. It is shown that for a given molecular volume and solvent dipole moment (or temperature) a spherical solute has the lowest excess chemical potential and hence the highest solubility, while a prolate solute with aspect ratio $x$ should be more soluble than an oblate solute with aspect ratio $1/x$. For a given solute molecule, the excess chemical potential increases with increasing temperature; this same trend is observed in the case of hydrophobic solvation. To help interpret the simulation results, comparison is made with a scaled-particle theory that requires prior knowledge of a solute-solvent interfacial tension and the pure-solvent equation of state, which parameters are obtained from simulation results for spherical solutes. The theory shows excellent agreement with simulation results over the whole range of solute elongations considered.Comment: 10 pages, 10 figure

Infrared Optical Properties of Ferropericlase (Mg1-xFexO): Experiment and Theory

The temperature dependence of the reflectance spectra of magnesium oxide (MgO) and ferropericlase (Mg1-xFexO, for x=0.06 and x=0.27) have been measured over a wide frequency range (~50 to 32000 cm-1) at 295 and 6 K. The complex dielectric function has been determined from a Kramers-Kronig analysis of the reflectance. The spectra of the doped materials resembles pure MgO in the infrared region, but with much broader resonances. We use a shell model to calculate the dielectric function of ferropericlase, including both anharmonic phonon-phonon interactions and disorder scattering. These data are relevant to understanding the heat conductivity of ferropericlase in the earth's lower mantle.Comment: 17 pages, 6 figure

A Review of Discrete Element Method (DEM) Particle Shapes and Size Distributions for Lunar Soil

As part of ongoing efforts to develop models of lunar soil mechanics, this report reviews two topics that are important to discrete element method (DEM) modeling the behavior of soils (such as lunar soils): (1) methods of modeling particle shapes and (2) analytical representations of particle size distribution. The choice of particle shape complexity is driven primarily by opposing tradeoffs with total number of particles, computer memory, and total simulation computer processing time. The choice is also dependent on available DEM software capabilities. For example, PFC2D/PFC3D and EDEM support clustering of spheres; MIMES incorporates superquadric particle shapes; and BLOKS3D provides polyhedra shapes. Most commercial and custom DEM software supports some type of complex particle shape beyond the standard sphere. Convex polyhedra, clusters of spheres and single parametric particle shapes such as the ellipsoid, polyellipsoid, and superquadric, are all motivated by the desire to introduce asymmetry into the particle shape, as well as edges and corners, in order to better simulate actual granular particle shapes and behavior. An empirical particle size distribution (PSD) formula is shown to fit desert sand data from Bagnold. Particle size data of JSC-1a obtained from a fine particle analyzer at the NASA Kennedy Space Center is also fitted to a similar empirical PSD function

Secondary organic aerosol formation from in-use motor vehicle emissions using a potential aerosol mass reactor.

Secondary organic aerosol (SOA) formation from in-use vehicle emissions was investigated using a potential aerosol mass (PAM) flow reactor deployed in a highway tunnel in Pittsburgh, Pennsylvania. Experiments consisted of passing exhaust-dominated tunnel air through a PAM reactor over integrated hydroxyl radical (OH) exposures ranging from ∼ 0.3 to 9.3 days of equivalent atmospheric oxidation. Experiments were performed during heavy traffic periods when the fleet was at least 80% light-duty gasoline vehicles on a fuel-consumption basis. The peak SOA production occurred after 2-3 days of equivalent atmospheric oxidation. Additional OH exposure decreased the SOA production presumably due to a shift from functionalization to fragmentation dominated reaction mechanisms. Photo-oxidation also produced substantial ammonium nitrate, often exceeding the mass of SOA. Analysis with an SOA model highlight that unspeciated organics (i.e., unresolved complex mixture) are a very important class of precursors and that multigenerational processing of both gases and particles is important at longer time scales. The chemical evolution of the organic aerosol inside the PAM reactor appears to be similar to that observed in the atmosphere. The mass spectrum of the unoxidized primary organic aerosol closely resembles ambient hydrocarbon-like organic aerosol (HOA). After aging the exhaust equivalent to a few hours of atmospheric oxidation, the organic aerosol most closely resembles semivolatile oxygenated organic aerosol (SV-OOA) and then low-volatility organic aerosol (LV-OOA) at higher OH exposures. Scaling the data suggests that mobile sources contribute ∼ 2.9 ± 1.6 Tg SOA yr(-1) in the United States, which is a factor of 6 greater than all mobile source particulate matter emissions reported by the National Emissions Inventory. This highlights the important contribution of SOA formation from vehicle exhaust to ambient particulate matter concentrations in urban areas

Reducing Urinary Catheter Use: A Protocol for a Mixed Methods Evaluation of an Electronic Reminder System in Hospitalised Patients in Australia

Introduction: Despite advances in infection prevention and control, catheter-associated urinary tract infections (CAUTIs) are common and remain problematic. Prolonged urinary catheterisation is the main risk factor for development of CAUTIs; hence, interventions that target early catheter removal warrant investigation. The study’s objectives are to examine the efficacy of an electronic reminder system, the CATH TAG, in reducing urinary catheter use (device utilisation ratio) and to determine the effect of the CATH TAG on nurses’ ability to deliver patient care. Methods and analysis: This study uses a mixed methods approach in which both quantitative and qualitative data will be collected. A stepped wedge randomised controlled design in which wards provide before and after observations will be undertaken in one large Australian hospital over 24 weeks. The intervention is the use of the CATH TAG. Eligible hospital wards will receive the intervention and act as their own control, with analysis undertaken of the change within each ward using data collected in control and intervention periods. An online survey will be administered to nurses on study completion, and a focus group for nurses will be conducted 2 months after study completion. The primary outcomes are the urinary catheter device utilisation ratio and perceptions of nurses about ease of use of the CATH TAG. Secondary outcomes include a reduced number of cases of catheter-associated asymptomatic bacteriuria, a reduced number of urinary catheters inserted per 100 patient admissions, perceptions of nurses regarding effectiveness of the CATH TAG, changes in ownership/interest by patients in catheter management, as well as possible barriers to successful implementation of the CATH TAG

Dipole Interactions and Electrical Polarity in Nanosystems -- the Clausius-Mossotti and Related Models

Point polarizable molecules at fixed spatial positions have solvable electrostatic properties in classical approximation, the most familiar being the Clausius-Mossotti (CM) formula. This paper generalizes the model and imagines various applications to nanosystems. The behavior is worked out for a sequence of octahedral fragments of simple cubic crystals, and the crossover to the bulk CM law is found. Some relations to fixed moment systems are discussed and exploited. The one-dimensional dipole stack is introduced as an important model system. The energy of interaction of parallel stacks is worked out, and clarifies the diverse behavior found in different crystal structures. It also suggests patterns of self-organization which polar molecules in solution might adopt. A sum rule on the stack interaction is found and tested. Stability of polarized states under thermal fluctuations is discussed, using the one-dimensional domain wall as an example. Possible structures for polar hard ellipsoids are considered. An idea is formulated for enhancing polarity of nanosystems by intentionally adding metallic coatings.Comment: 18 pages (includes 6 embedded figures and 3 tables). New references, and other small improvements. Scheduled for publication by J. Chem. Phys., Jan. 200