The kinetics of the isothermal decomposition of a series of compounds are studied using electron paramagnetic resonance spectroscopy. The general formula for the compounds under investigation is the guest chromophore, {Cr(NH(,3))(,5)X}('2+) doped into the isomorphous host material, {M(NH(,3))(,5)Y}Z(,2), where X = Cl or Br, M = Co or Rh, Y = Cl or Br, and Z = Cl('-), Br('-), I('-), N(,3)('-), or NO(,3)('-). All of the investigated displayed first order kinetics and excellent adherence to the Arrhenius law. The observations, including the activation energies and frequency factors, are presented for each system. Also displayed are the Arrhenius diagrams for each decomposition as well as pre- and post-reaction spectra. Several trends emerge from the data and these are discussed and possible explanations of the observables are offered. Lastly, several possible avenues of continued endeavor are suggested. / Source: Dissertation Abstracts International, Volume: 45-09, Section: B, page: 2929. / Thesis (Ph.D.)--The Florida State University, 1984.

Cyclonic ring interaction with the Gulf Stream recirculation is studied numerically using a two-layer quasigeostrophic model. Rings shed by the Gulf Stream in previous eddy-resolving general circulation experiments of Holland move westward, embedded in the recirculation. We find that these rings, when transferred to quiescent surroundings, have a nearly steady northward translation component, suggesting steering by the recirculation. Quasi-Lagrangian vorticity balances show that, if an isolated ring decays by Rossby wave dispersion, northward translation is required for potential vorticity conservation. / Although stable westward channel flows comparable to the recirculation failed to inhibit northward translation, a current that appeared to be barotropically unstable substantially reduced it. Energy extraction probably offset decay, reducing the need for planetary vorticity addition. / The trajectories in the general circulation model comprise two phases. Southward translation, after apparent separation, occurs in a region found baroclinically unstable by previous investigators. The ring continues to grow in area and relative vorticity. Decay characterizes the later phase. / The channel rings adjusted after a month to a quasi-steady deep potential vorticity configuration. A wedge of fluid intrudes the region below the ring from the south. The exiting fluid overshoots its undisturbed latitude, leaving a well-mixed wake. A somewhat weaker "deep eddy wedge" appears in general circulation experiments. / We find that moderate bottom slope can alter the deep potential vorticity distribution, preventing wedge formation. Deep potential vorticity influence on upper eddy dynamics may be critically related to potential vorticity homogenization and the structure of the thermocline. / Source: Dissertation Abstracts International, Volume: 45-11, Section: B, page: 3454. / Thesis (Ph.D.)--The Florida State University, 1984.

The purpose of this study was to trace, reconstruct, and record the facts, which reflect the development, growth, and continuity of the physical education program at Florida State University, from its beginning through 1978. / Traditional methods of historical research were utilized to locate and investigate primary and secondary sources. A substantial amount of information was obtained from personal interviews with former students and former and present faculty members. Photographs, scrapbooks, personal files containing letters and memorandums, local and college newspapers, college yearbooks, college catalogs and bulletins, and department minutes also provided valuable information. / Investigation revealed that the early physical education program, under the leadership of Katherine Montgomery, gained widespread respect as a vital part of the all-women's college. The college became coeducational in 1947, and a men's department, headed by Howard Danford, was added. Later the men's and women's programs combined, under the leadership of Kenneth Miller. By the mid-1960s the department was conducting a broad-in-scope program which had reached a point of national prominence. From that point there began a splintering process of the various functions conducted by the department until by the conclusion of this study only the teacher preparation phase survived. / The major events contributing toward the specific evolutionary pattern of the department through 1978 were: (1) the dedicated, career-long commitment of Katherine Montgomery, which established a sound basis for the progressive growth of the department's professional teacher training program; (2) the relatively brief but stimulating tenure of Howard Danford who would not be satisified with mediocrity; (3) the combining of the women's department with the men's department in 1947--a situation which had to be, but which, regrettably, resulted in continuous trauma, and which was perhaps the single most important factor in preventing the achievement of the department's full potential; (4) the opposition of a small, but determined, group in the faculty senate, which harassed that body to a point at which the senate shifted its position of strong support to one of eliminating the required physical education program; and, finally, (5) the unaccountable lack of administrative support by a series of deans and presidents who would not back up their off-the-record advocacy with public endorsement. / Source: Dissertation Abstracts International, Volume: 41-07, Section: A, page: 2993. / Thesis (Ph.D.)--The Florida State University, 1980.

Two versions of an x-y-t, two-layer, numerical model with realistic coastline and bottom topography on a rotated (beta)-plane are used to study the upwelling system off the Peruvian coast. A hydrodynamic version of the model with two homogeneous layers is used to examine the interaction between the bottom topography and coastal trapped waves. / The fluctuations in the undercurrent off the Peruvian coast have been shown (Smith, 1978) to be uncorrelated with the local winds. The hypothesis proposed by Smith is that these fluctuations are the result of coastal trapped Kelvin waves. A parameterization scheme, based on Kelvin wave dynamics is introduced to simulate these coastal trapped waves. The relationship between bottom topographic features and the pycnocline height anomalies for a longshore current event is then examined. The principle of conservation of potential vorticity is used to explain the interactions between the waves and the bottom topography. The results of the hydrodynamic model shows that the interaction between a propagating waves and the bottom topography can play a significant role in determining the location of the centers of enhanced upwelling. / A thermodynamic version of the model, one in which the layer averaged densities are predicted variables, it used to extend the information available from the hydrodynamic models. A parameterization scheme for the interfacial mixing is introduced. There is a twofold reason for introducing thermodynamic and mixing into the model. The first is to include physics normally neglected in upwelling models. The second is to provide a physical mechanism to keep the interface from surfacing. The locations of the centers of enhanced upwelling as indicated by the interface displacement and sea surface temperature are examined and compared to observed data. The results of the thermodynamic model show that a positive heat flux is required to balance the large scale wind induced upwelling in order to observe the centers of enhanced upwelling due to internal waves/bottom topography interaction. / The local wind forcing for both versions of the model are derived from meteorological buoy wind observations. The time series of wind observations from Pacific Marine Environmental Laboratory's (PMEL) PSS-mooring during March, April, May (MAM) 1977 are used to construct the time-dependent amplitudes for the wind function. / Source: Dissertation Abstracts International, Volume: 42-01, Section: B, page: 0121. / Thesis (Ph.D.)--The Florida State University, 1980.

An expression is derived for the charge density susceptibility which, under the Unsold approximations, reduces to the Fourier transforms of electron density functions. When considering uncorrelated wavefunctions, the susceptibility is given simply by static form factors in terms of which the second order Coulomb energy may be calculated. This is equivalent to applying the Unsold approximations directly unto the second order Coulomb energy expression in the usual time independent Rayleigh-Schrodinger perturbation theory. / Using the interactions of hydrogen-hydrogen and helium-helium diatoms as test cases, we evaluated numerically and analytically the various integrals for their second order dispersion energies. The two approaches differ in that while the latter requires analytic form factors, the former can use both analytic as well as the readily available tabulated form factors. Their results are found to be in excellent agreements. / Appropriate choices for the Unsold average excitation energy are made to put the values of the dispersion energy on an absolute scale. Precise potentials at large separations are obtained. By adding to our dispersion energy the first order Coulomb, exchange and second order induction contributions, the whole potential curves too agree remarkably well with previous accurate results. / The present treatment allows the use of the full Coulomb potential without recourse to the multipole expansion. In addition, the formulation in momentum space affords considerable mathematical simplification. / Source: Dissertation Abstracts International, Volume: 42-06, Section: B, page: 2392. / Thesis (Ph.D.)--The Florida State University, 1981.

7-Azaindole is a molecule which undergoes excited-state proton-transfer in alcohol solvents (12). Tautomer luminescence arises from double-proton-transfer in a cyclical hydrogen-bonded complex between 7-azaindole and one alcohol molecule. The lack of 7-azaindole tautomer luminescence in water solvents is thought to be unusual since alcohol and water are both hydroxyllic solvents. We have shown that tautomer fluorescence can be detected in ether solutions that have been saturated with water. The position of the fluorescence is identical to that in ethanol. The formation of the hydrogen-bonded 7-azaindole complex in dilute water solutions has been attributed to the presence of monomer and small clusters of water molecules in these dilute solutions. In liquid water 7-azaindole cannot effectively compete with the extended network of water hydrogen bonds for monomeric water, and excited-state proton-transfer cannot occur. / We also have proposed that the excited 7-azaindole can form an exciplex with one alcohol molecule. This exciplex is directly analogous to the indole:alcohol exciplex (33) in a number of ways. Dramatic quenching of the exciplex luminescence can be explained by postulating the ejection of an electron by the exciplex upon deactivation. We have found luminescence yield effects and picosecond lifetime dependences on the acidity and state of aggregation of the alcohol which support this hypothesis. A deuterium isotope effect also has been observed. / 3-Hydroxyflavone can undergo intramolecular excited-state proton-transfer in hydrocarbon solvents. 5-Hydroxyflavone, however, exhibits no luminescence under similar conditions. An investigation of the extinction coefficients of these molecules and flavone, in addition to their luminescence properties and resonance Raman spectra, has allowed us to propose that in hydrocarbon solvents, the ('1)n, (pi)* state is lowest in flavone, the ('1)n, (pi)* state and the ('1)(pi), (pi)* state are degenerate in 5-hydroxyflavone, and that the ('1)(pi), (pi)* is lowest in 3-hydroxyflavone. The consequence of the degeneracy of the first two excited states in 5-hydroxyflavone results in a pseudo Jahn-Teller Splitting and rapid radiationless transition to the ground state. / Source: Dissertation Abstracts International, Volume: 42-10, Section: B, page: 4076. / Thesis (Ph.D.)--The Florida State University, 1981.

Source: Dissertation Abstracts International, Volume: 40-10, Section: A, page: 5366. / Thesis (Ph.D.)--The Florida State University, 1979.

Source: Dissertation Abstracts International, Volume: 40-10, Section: A, page: 5367. / Thesis (Ph.D.)--The Florida State University, 1979.

A survey of the forces acting on and in molecules and the relation of these forces to molecular spectroscopic investigations is presented. New results, both experimental and theoretical, are presented which demonstrate aspects of these forces. / The experimental results are the observation of quenching of tautomer fluorescence and normal phosphorescence of 7-azaindole H-bonded complexes in dipolar solvents. The former observation is obtained at room temperature and is observed when the concentration of an alcohol is varied with a fixed concentration of 7-axaindole in a hydrocarbon solvent. The latter observartion is obtained when solutions of 7-azaindole in dipolar solvents are cooled slowly as opposed to fast cooling with liquid nitrogen. These observations are attributed to local forces resulting from dipolar solvent cages around the H-bonded complexes. / The theoretical results are that, due to currents within molecules, the Hellmann-Feynman theorem fails at the 10-ppm level of accuracy. The general non-quantum-electrodynamical form of the non-electrostatic forces responsible for this failure is derived. The general results are applied to the molecule HD('+) for which the first-order perturbation theoretical correction due to these forces to the 1-0 vibrational transition energy for the ground electronic state is calculated. The value obtained is -0.072 cm('-1). This value agrees with the experimental minus theoretical energy difference obtained if the theoretical calculations neglects these forces. / Source: Dissertation Abstracts International, Volume: 41-03, Section: B, page: 0972. / Thesis (Ph.D.)--The Florida State University, 1980.

A general theory of spin relaxation developed by Fulton is applied to the problem of rotational relaxation of a dipole rotating in two dimensions. The model system is composed of a rotor with dipole moment (mu) at the center of a circular cavity in a continuous, infinite dielectric medium (heat bath). We write a quantum-mechanical Hamiltonian for the system which contains a term for free rotor motion and a bath-rotor interaction term. An equation of motion for the operators describing the rotor is developed using Heisenberg's equation of motion in conjunction with the theory of functionals. This equation is taken in the classical limit by assuming that the rotor's rotational spacing is small. We choose a simple form for the free motion time dependence of the classical rotor functions and thereby identify the rotor functions with the eigenfunctions of the Liouville operator. Through consideration of the bath-rotor interaction we find the relevant bath functions to be the bath's electric field components at the center of the cavity. The classical equation of motion which results from this process describes the time dependence of the probability distribution for the rotor's angular momentum. This equation resembles a Fokker-Planck equation with a diffusion coefficient which depends upon the angular momentum. We find that this coefficient is related to the fluctuations of the bath's electric field in the cavity. The equation of motion is solved numerically by finite differences. The solution, corresponding to relaxation of a small molecule from a high initial angular momentum state, shows a double-maximum or "bimodal" shape for intermediate momentum values before relaxing to the equilibrium Boltzman distribution. This behaviour is qualitatively similar to experimental time-dependent angular momentum distributions found by Polanyi and co-workers for hydrogen / halides formed in molecular beam reactions. We also derive and solve numerically an equation of motion for the orientational correlation function of the rotor. / Source: Dissertation Abstracts International, Volume: 42-06, Section: B, page: 2388. / Thesis (Ph.D.)--The Florida State University, 1981.