The virial equation of state p = ρRT[ 1 + B(T) ρ + C(T) ρ2 + · · ·] for high pressure and density gases is used for computing chemical equilibrium properties and mixture compositions of strong shock and detonation waves. The second and third temperature-dependent virial coefficients B(T) and C(T) are included in tabular form in computer codes, and they are evaluated by polynomial interpolation. A very accurate numerical integration method is presented for computing B(T) and its derivatives for tables, and a sophisticated method is introduced for interpolating B(T) more accurately and efficiently than previously possible. Tabulated B(T) values are non-uniformly distributed using an adaptive grid, to minimize the size and storage of the tables and to control the maximum relative error of interpolated values. The methods introduced for evaluating B(T) apply equally well to the intermolecular potentials of Lennard-Jones in 1924, Buckingham and Corner in 1947, and Rice and Hirschfelder in 1954.

Las sales de oro se han convertido en uno de los catalizadores por excelencia en una gran variedad de transformaciones orgánicas mediante la activación selectiva de alquinos, alenos y alquenos. Parte del trabajo de esta tesis doctoral se ha centrado en el estudio de la naturaleza carbénica o carbocatiónica de los intermedios de reacción presentes en las cicloisomerizaciones de 1,5-eninos catalizadas por complejos de oro. De esta forma se han desarrollado distintas metodologías de ciclación dando lugar a diferentes productos tricíclicos a partir de oxo-1,5-eninos o 1,5-bencileninos. Además, se ha podido aplicar estas nuevas metodologías de ciclación en la síntesis de productos naturales como etapa clave de la misma. Por último, nuestro interés se ha centrado en el desarrollo de reacciones intermoleculares de gran utilizad química catalizadas por oro. Por ello hemos desarrollado la síntesis de fenoles substituidos a partir de diferentes acetilenos y furanos. / Gold salts and complexes are the most active catalysts for the activation of alkynes, allenes and alkenes. Part of this Doctoral Thesis is focused on the study of the carbenic or cationic character of the reaction intermediates presents in the cycloisomerizations of 1,5-enynes catalyzed by goldcomplexes. Different methodologies have been developed to synthesize different tryciclic products from oxo-1,5-enynes or 1,5-benzylenynes. Moreover, these methodologies were applied successfully as the key step in the synthesis of natural products. Finally, our interest was focused on the development of intermolecular gold-catalyzed reactions. Therefore, we have developed a general synthesis of trisubstituted phenols from alkynes and furans.

As the demand for high performance small electronic devices has increased, heat removal from these devices for space use is approaching critical limits. A heat pipe is a promising device to enhance the heat removal performance due to the phase change phenomena for space thermal management system. Even though a heat pipe has a big potential to remove the thermal energy from a high heat flux source, the heat removal performance of heat pipes cannot be predicted well since the first principle of evaporation has not been established. The purpose of this study is to establish a method to apply the evaporation model based on the statistical rate theory for engineering application including vapor-liquid-structure intermolecular effect. The evaporation model is applied to the heat pipe performance analysis through a pressure balance and an energy balance in the loop heat pipe.

Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

In this thesis, I present a comprehensive study of the interfacial electronic structure and thin film growth of two types of dipolar organic semiconductors on noble metals by employing a surface science approach, which underlines the critical role of surface electronic states in determining the interfacial electronic structure and self-assembly of organic semiconductors. I show that the electronic structure at organic/metal interfaces is complex and depends on important factors such as molecular adsorption configuration, surface/molecule coupling strength, reactivity of the substrate, molecular electrostatics, and local film structure. I demonstrate the fundamental capability of the image potential states and resonances in probing the local film environment, especially in systems consisting of inhomogeneous film structure. I also show that the presence of adsorbates on a surface allows one to investigate quantum mechanical interference effects otherwise not accessible on the bare surface. The dipolar organic semiconductors studied here are vanadyl naphthalocyanine (VONc) and chloroboron-subphthalocyanine (ClB-SubPc). The single crystals of gold and copper with hexagonal surface symmetry (111) were used to investigate the interfacial properties of VONc and ClB-SubPc, respectively. The fundamental understanding of self-assembly of large π-conjugated organic semiconductors on metals is a crucial step in controlling fabrication of supramolecular structures. Here, I provide a first step in this direction with a detailed and quantitative analysis of molecular nearest-neighbor distances that unravels the fundamental intermolecular interactions of organic semiconductors on transition metal surfaces. I additionally investigated the interfacial electronic structure of these organic semiconductors to examine the relation between molecular adsorption orientation and charge transfer across the interface.

The metallic binary-alloy fuel Uranium-Zirconium is important for use in the new generation of advanced fast reactors. Uranium-Zirconium goes through a phase transition at higher temperatures to a (gamma) Body Centered Cubic (BCC) phase. The BCC high temperature phase is particularly important since it corresponds to the temperature range in which the fast reactors will operate. A semi-empirical Modified Embedded Atom Method (MEAM) potential is presented for Uranium-Zirconium. This is the first interatomic potential created for the U-Zr system. The bulk physical properties of the Uranium-Zirconium binary alloy were reproduced using Molecular Dynamics (MD) and Monte Carlo (MC) simulations with the MEAM potential. The simulation of bulk metallic alloy separation and ordering phenomena on the atomic scale using iterative MD and MC simulations with interatomic potentials has never been done before. These simulations will help the fundamental understanding of complex phenomena in the metallic fuels. This is a large step in making a computationally acceptable fuel performance code, able to replicate and predict fuel behavior.

A new intermolecular potential energy surface, rovibrational transition frequencies, and line strengths are computed for OCS-OCS and CO2-CS2. The potentials were made by fitting energies obtained from explicitly correlated coupled-cluster calculations and fit using an interpolating moving least squares method. Rovibrational transition frequencies are also calculated for four isotopologues of the N2O dimer using a previously presented potential energy surface. The rovibrational Schroedinger equation for all three dimers is solved with a symmetry-adapted Lanczos algorithm and an uncoupled product basis set. All four intermolecular coordinates are included in the calculation. On the OCS-OCS potential energy surface, a previously unknown, cross-shaped isomer is found along with polar and non-polar isomers. For CO2-CS2, the previously found cross-shaped minima is found along with a slipped-parallel configuration. The associated wavefunctions and energy levels for each of these isomers is presented. To identify states that have a permanent dipole, both calculations of line strengths and vibrational parent analysis is used. For non polar states of, OCS-OCS, and N2O-N2O isotopologues, and all CO2-CO2 states, only vibrational parent analysis was used. Calculated rotational constants differ from their experimental counterparts by less than 0.001 wavenumbers for OCS-OCS and CO2-CS2, and less than 0.002 wavenumbers for any N2O-N2O isotopologue. / Thesis (Master, Physics, Engineering Physics and Astronomy) -- Queen's University, 2012-08-23 13:19:45.294

There are currently three known crystal packing motifs of boronsubphthalocyanine derivatives. Each motif is associated with a particular class of BsubPc derivatives, and none are ideal for organic electronic applications according to the criteria we defined for evaluation: having a continuous pathway for charge-carrier conduction in the solid-state, resistance to hydrolysis, good electrochemical and optical properties, and possession of a robust crystal form. In this thesis, we present five methods for altering the crystal packing structure of phenoxy-BsubPc derivatives in order to meet the above four criteria. We find that neither addition of steric bulk to the axial derivative nor changing the symmetry of the compounds is sufficient for creating a new crystal packing motif. We do find that reducing the symmetry of the axial group does increase the solubility greatly, however. We identify a new motif for BsubPc crystals that occurs when the intermolecular interactions between the axial phenoxy segment and the BsubPc ligand are increased. We present two methods for achieving this new motif, one is through addition of a π-Br interaction and the other is through creation of a strong π-acid/ π-base stacking by making the axial phenoxy more π-electron rich. Unfortunately, the p-bromophenoxy-BsubPc forms this new motif as a kinetic product, isolation of which is unreliable. Attaching a naphthol fragment axially to the BsubPc creates a stable version of this new motif. We also synthesized a new class of BsubPc pseudohalides based on sulfonate derivatives. Of the derivatives in this new class, we found that mesylate-BsubPc forms into a crystal packing structure that possesses a one-dimensional pathway for charge carrier mobility, but is still resistant to hydrolysis under the conditions tested. Overall, we show four compounds that meet the criteria for further study as organic electronic materials: p-methoxyphenoxy-BsubPc, α-naphthoxy-BsubPc, β-naphthoxy-BsubPc, and mesylate-BsubPc.

There are currently three known crystal packing motifs of boronsubphthalocyanine derivatives. Each motif is associated with a particular class of BsubPc derivatives, and none are ideal for organic electronic applications according to the criteria we defined for evaluation: having a continuous pathway for charge-carrier conduction in the solid-state, resistance to hydrolysis, good electrochemical and optical properties, and possession of a robust crystal form. In this thesis, we present five methods for altering the crystal packing structure of phenoxy-BsubPc derivatives in order to meet the above four criteria. We find that neither addition of steric bulk to the axial derivative nor changing the symmetry of the compounds is sufficient for creating a new crystal packing motif. We do find that reducing the symmetry of the axial group does increase the solubility greatly, however. We identify a new motif for BsubPc crystals that occurs when the intermolecular interactions between the axial phenoxy segment and the BsubPc ligand are increased. We present two methods for achieving this new motif, one is through addition of a π-Br interaction and the other is through creation of a strong π-acid/ π-base stacking by making the axial phenoxy more π-electron rich. Unfortunately, the p-bromophenoxy-BsubPc forms this new motif as a kinetic product, isolation of which is unreliable. Attaching a naphthol fragment axially to the BsubPc creates a stable version of this new motif. We also synthesized a new class of BsubPc pseudohalides based on sulfonate derivatives. Of the derivatives in this new class, we found that mesylate-BsubPc forms into a crystal packing structure that possesses a one-dimensional pathway for charge carrier mobility, but is still resistant to hydrolysis under the conditions tested. Overall, we show four compounds that meet the criteria for further study as organic electronic materials: p-methoxyphenoxy-BsubPc, α-naphthoxy-BsubPc, β-naphthoxy-BsubPc, and mesylate-BsubPc.