Physical Sciences and Mathematics Commons^™

Termolecular Proton Transfer Reactions Assisted By Ionic Hydrogen Bond Formation: Reactions Of Aromatic Cations With Polar Molecules, George M. Daly, Michael Mautner, Y. B. Pithawalla, M. Samy El-Shall

Chemistry Publications

We present a new method that applies resonant‐two‐photon ionization to generate reactant ions selectively in the source of a high‐pressure mass spectrometer (R2PI‐HPMS) for kinetic and equilibrium studies. Applications to reactions that would be obscured otherwise in a complex system are illustrated in mixtures of benzene with polar solvent molecules (S). We observe a novel type of proton transferreactions from C₆H₆ ^+• to two S molecules where S=CH₃CN, CH₃OH, C₂H₅OH and CH₃COOC₂H₅, and from C₆H₅CH₃ ^+• to two …

Oxidation States And Magnetism Of Fe Nanoparticles Prepared By A Laser Evaporation Technique, B. J. Jönsson, T. Turkki, V. Ström, M. S. El-Shall, K. V. Rao

Chemistry Publications

Nanoparticles of iron and iron oxide have been prepared in a thermal diffusion cloud chamber using pulsed laser evaporation. SEM/TEM studies of these particles reveal a size distribution with a mean diameter of about 60 Å. This is consistent with the mean particle size estimated from the magnetic data. The oxidation levels of these nanoparticles prepared at different partial oxygen pressures were investigated using FTIR. All the samples are found to exhibit superparamagnetism with blocking temperatures ranging from 50 K to above room temperature. Magnetic anisotropy constants are calculated from the frequency dependence of the blocking temperatures are found to …

Condensation Of Supersaturated Vapors Of Hydrogen Bonding Molecules: Ethylene Glycol, Propylene Glycol, Trimethylene Glycol, And Glycerol, David B. Kane, M. Samy El-Shall

Chemistry Publications

The critical supersaturations required for the homogeneous nucleation (rate of 1 drop cm⁻³ s⁻¹) of ethylene glycol, propylene glycol, trimethylene glycol and glycerol vapors have been measured over wide temperature ranges (e.g., 280–400 K) using an upward thermal diffusion cloud chamber. At lower temperatures the experimental nucleation rates are much higher than the predictions of the classical nucleation theory. Glycerol shows the best agreement between experiment and theory in the temperature range of 340–370 K. An apparent increase in the critical supersaturation of glycerol is observed with increasing carrier gas (helium) pressure and this effect is more …

A Monte Carlo Study Of Methanol Clusters (Ch3oh)N, N=5-256, D. Wright, M. S. El-Shall

Chemistry Publications

The thermodynamic and structural properties of methanol clusters (CH₃OH) _N , N=5–15, 20, 30, 60, 128, 256 and the bulk liquid have been investigated using Monte Carlo simulation. Calculated properties as a function of size include electrostatic and dispersive contributions to the configurational energy, configurational heat capacities,fractal dimension, density profiles, order parameters characterizing dipole and bond vector orientation, and the Lindemann index. The clusterheat capacities as a function of N possess an interior maximum near N=128 and converge to the bulk value from above. Monocyclic, semiplanar structures are found to persist at liquidlike temperatures up to …

Space-Based Genetic Cryoconservation Of Endangered Species, Michael Noah Mautner

Chemistry Publications

Genetic materials of endangered species must be maintained, for cryoconservation, permanently near liquid nitrogen temperatures below 77 K. Due to the instability of human institutions, permanent safety is best provided at storage sites that maintain passively the needed low temperatures, and provide barriers to access. The required conditions are available in permanently shaded polar lunar craters with equilibrium temperatures of 8 to 40 K, on the moons of Saturn, and unshielded storage satellites. A genetic depository can be incorporated readily into planned lunar programmes.

Equilibrium Structure And Bonding Of Small Iron-Carbon Clusters, Beth K. Nash, B. K. Rao, Puru Jena

Physics Publications

The equilibrium geometries, binding energies, and electronic structure of neutral FeC _n (n≤3) clusters have been calculated self‐consistently using ab initio molecular orbital theory. The exchange and correlation contributions to the total energy were computed using both the density functional method (with and without nonlocal correction) as well as the Hartree–Fock–Möller–Plesset theory. All levels of theory predict the equilibrium geometries to be cyclic. The binding energies, bond lengths, and the Mulliken charges obtained from both methods of calculations are also in agreement. The results are compared with recent mobility and photoelectron spectroscopy experiments.

Development Of Quasi-Likelihood Techniques For The Analysis Of Pseudo-Proportional Data, Jennifer A. Elder

Theses and Dissertations

In certain experimental situations, the data observed are pseudo-proportional. By this, we observe the numerator, the number of responders, but the denominator, the total number, is random and, possibly, unobserved. In such situations, the data often exhibit "extra" variability due to the randomness of the denominator. Analysis of these data should account for this overdispersion. Several authors have proposed parametric approaches to this problem. Finney [Biometrika (1949) 36, 239-256] proposed the use of a mixture of the binomial and Poisson distributions. Anscombe [Annals of Applied Biology (1949) 36, 203-205] discussed the use of a mixture of the binomial and negative …

Power Analysis For The Mixed Linear Model, Cheryl Annette Dixon

Theses and Dissertations

Power analysis is becoming standard in inference based research proposals and is used to support the proposed design and sample size. The choice of an appropriate power analysis depends on the choice of the research question, measurement procedures, design, and analysis plan. The "best" power analysis, however, will have many features of a sound data analysis. First, it addresses the study hypothesis, and second, it yields a credible answer.

Power calculations for standard statistical hypotheses based on normal theory have been defined for t-tests through the univariate and multivariate general linear models. For these statistical methods, the approaches to power …

Interactions Among The Stationary Phase, The Mobile Phase, And The Solute In Liquid Chromatographic Systems, Zengbiao Li

Theses and Dissertations

Interactions among the stationary phase, the mobile phase, and the solute in liquid chromatography' have been studied. A strong dependence of the stationary phase properties on the mobile phase composition may arise from their interactions.

The solvatochromic comparison method, which can give estimates for the dipolarity-polarizability, the hydrogen-bonding acidity, and the hydrogen-bonding basicity of a solvent, represented by the solvatochromic parameters π⁺, α and β, respectively, was used to study the surface properties of silica in the presence of n-hexane-chloroform or n-hexane-ethyl ether mixtures. A high dipolarity- polarizability, a high hydrogen-bonding acidity, and a low hydrogen-bonding basicity …