Source: Dissertation Abstracts International, Volume: 27-08, Section: B, page: 2670. / Thesis (Ph.D.)--The Florida State University, 1966.

Source: Dissertation Abstracts International, Volume: 28-05, Section: B, page: 1873. / Thesis (Ph.D.)--The Florida State University, 1967.

Source: Dissertation Abstracts International, Volume: 20-06, page: 2037. / Thesis (Ph.D.)--The Florida State University, 1959.

Source: Dissertation Abstracts International, Volume: 23-05, page: 1534. / Thesis (Ph.D.)--The Florida State University, 1962.

Source: Dissertation Abstracts International, Volume: 25-12, page: 6987. / Thesis (Ph.D.)--The Florida State University, 1964.

Source: Dissertation Abstracts International, Volume: 26-12, page: 7067. / Thesis (Ph.D.)--The Florida State University, 1966.

The following endoergic ion-molecule reactions were investigated with a crossed beam apparatus: (UNFORMATTED TABLE FOLLOWS) / Cs('+) + C(,6)H(,5)CN (--->) C(,6)H(,5)('+) + CsCN (1) / Cs('+) + C(,4)H(,7)Cl (--->) C(,4)H(,7)('+) + CsCl (2) / (--->) C(,3)H(,5)('+) + C(,2)H(,2) + CsCl (3) / Cs('+) + C(,3)H(,5)Br (--->) C(,3)H(,5)('+) + CsBr (4)(TABLE ENDS) / Angular and energy distributions were measured for these reactions at the following relative collision energies: reaction (1) at 10.9 and 13.1 eV, reaction (2) at 7.2 eV, reaction (3) at 9.9 eV, and reaction (4) at 7.2 and 9.5 eV. / Cartesian contour maps of the relative scattering intensity of the product ion were constructed for each reaction at each relative collision energy. The experimental contour maps for reactions (1) through (3) showed the greatest scattering intensity sideways to the center of mass, unlike the results of other similar systems investigated in this lab. The experimental contour map for reaction (4) showed backward peaking. / A general treatment of the Sequential Impulse Model (SIM) was developed for endoergic, exoergic and elastic reactions and generic calculated contour maps were presented to illustrate the effects of the model's adjustable parameters. Best fit calculated SIM contour plots were presented for reactions (1), (2) and (4). Contour maps of the relative intensity of the scattered product ion for reactions (1) and (2) were reproduced quite successfully, while the corresponding contour maps for reaction (4) were reproduced with fair success. / The SIM best fit calculations for reaction (1) were discussed in comparison with SIM calculations published for reactions of Cs('+) with other substituted benzenes. Physical and chemical implications of the SIM best fit parameters were discussed for each system. Finally, several modifications to the SIM were suggested to enhance the model's realism. / Source: Dissertation Abstracts International, Volume: 48-03, Section: B, page: 0772. / Thesis (Ph.D.)--The Florida State University, 1987.

In the theoretical part of this study, the thermodynamics of ionic hydration was considered. Hydration functions were assumed to consist of neutral and electrostatic terms. Neutral contributions were evaluated from noble gas solubility data. Mean Spherical Approximation equations, combined with the Stillinger ST-2 off-centered water dipole model, supplied values for the electrostatic functions. Calculated Gibbs free energies of hydration for several ions agreed with experiment. Discrepancies between the calculated and absolute values of entropies of hydration can be correlated with the structure breaking tendency of monovalent ions. / A tracer level solvent extraction technique was used to investigate ionic interactions in aqueous electrolytes. Am(III) was chosen as a test metal ion and a cation exchanger HDEHP as the extractant. From the activity coefficients, calculated by Pitzer's theory, and measured distribution ratios it was deduced that the ion pairing of Am(III) in single electrolytes with anion X('-) (X('-) is ClO(,4)('-), NO(,3)('-) and Cl('-)) first increases with the concentration of X('-), then decreases and finally rises again. The salting out phenomenon at intermediate concentrations was attributed to the energetically unfavored co-sphere overlap between Am(III) and X('-). / The extraction of Am(III) from constant ionic strength (1.00, 2.50 and 5.00 M) electrolyte mixtures was analyzed by the stability constant technique. Stoichiometric first stability constants for AmNO(,3)('2+) and AmClO(,3)('2+) were determined. Problems with the evaluation method were also discussed. As an alternative treatment of the data, an empirical equation of the form DELTA = i(,2)(1 - i(,2)) (u + (1 - 2i(,2))v was introduced, where DELTA is proportional to the reciprocal of the distribution ratio. Variation of the interaction parameters u and v can be interpreted in terms of the thermodynamic properties of the medium ions. Except when DELTA varies about zero, u and v vary consistently with the ionic stength, which allows for predictions of distribution ratios at untested ionic strengths and composition. / Source: Dissertation Abstracts International, Volume: 48-03, Section: B, page: 0776. / Thesis (Ph.D.)--The Florida State University, 1987.

The ground state properties and excited-state dynamics of two complex molecules of biological significance have been investigated experimentally by steady-state and picosecond transient absorption spectroscopy, and theoretically by molecular orbital calculations. Lumichrome (7,8-dimethylalloxazine), has been found to form a ground-state anion in p-dioxane and certain alcohol solvents. Picosecond transient absorption studies of lumichrome in acetic acid, pyridine, p-dioxane, methanol, and water at pH 9.8, as well as 1,3-dimethyllumichrome and lumiflavin in methanol solvents are reported. The picosecond transient absorption measurements of lumichrome in p-dioxane solvent revealed the presence of a ground-state and possibly excited-state anion, as well as a rapid risetime of $\rm T\sb{\rm n}\gets\rm T\sb1$ absorption of the normal molecule. Studies of lumichrome in methanol solvent indicate the occurrence of excited-state proton-ejection. Picosecond transient absorption experiments of lumichrome in acetic acid and in pyridine solvents suggested that excited-state proton transfer may be preceded by excited-state proton ejection. The absence of observed $\rm T\sb{\rm n}\gets\rm T\sb1$ absorption of the tautomer form of lumichrome in these solvents suggested that the triplet population of the isoalloxazine form may be rapidly depleted by semiquinone radical formation. / Possible radiationless deactivation pathways of the non-fluorescent molecule, 5-hydroxyflavone, have been investigated by steady-state and picosecond transient absorption spectroscopy, as well as by molecular orbital calculations. The specific solvent dependence of the steady-state absorption spectra of 5-hydroxyflavone reflects the previously-proposed strength of the intramolecular H-bond and suggests a strong vibronic coupling. A weakly-absorbing transient was observed beginning at ca. 50 ps in methanol solvent. Ab initio SCF molecular orbital calculations were performed on both the normal and tautomer forms of 5-hydroxyflavone. Ab initio SCF and geometry optimization, and semi-empirical INDO/S-CI calculations were performed on the small analog, 5-hydroxychromone. Results of these calculations, in conjunction with experimental results, suggest that two plausible mechanisms for radiationless pathways in 5-hydroxyflavone are a pseudo-Jahn-Teller effect, and a rapid intersystem crossing, both in the tautomer form of the molecule which is presumed to form via excited-state proton transfer. / Source: Dissertation Abstracts International, Volume: 48-09, Section: B, page: 2659. / Thesis (Ph.D.)--The Florida State University, 1987.

Excited-state proton transfer reactions are investigated for three different molecular species, 3-hydroxyflavone, 7-azaindole, and lumichrome. Both steady-state and picosecond spectroscopic techniques are used to establish the dominant role of solvent structure and dynamics in the tautomerization mechanisms of these systems. The explicit consideration of a ground-state hydrogen-bonding equilibrium together with the subsequent excited-state solvent/solute relaxation dynamics allows for a precise interpretation of the processes which occur in these molecules following electronic excitation. / Proton transfer in 3-hydroxyflavone is formally an intramolecular process. The tautomerization process in this molecule, however, is found to depend sensitively on interactions with the surrounding solvent molecules. Distinct ground-state species which give rise to different excited-state luminescence behavior are identified and characterized. In the absence of hydrogen-bonding perturbations the tautomerization in 3-hydroxyflavone is rapid, efficient, and effectively independent of both temperature and viscosity. / The isolated 7-azaindole molecule possesses no direct pathway for tautomerization. If proton transfer is to occur it must do so through a molecular bridge of some sort. This class of excited-state reactions is refered to as pseudointramolecular proton transfer to distinguish it from the purely intramolecular case. In alcoholic solvents the proton transfer in 7-azaindole takes place in cyclically hydrogen-bonded complexes. Although the physical mechanisms differ, the dynamical aspects of the tautomerization process in 7-azaindole are strikingly similar to those of 3-hydroxyflavone. The tautomerism is intimately coupled to the structure and dynamics of the surrounding solvent cage. / Lumichrome provides a particularly interesting case of pseudo-intramolecular proton transfer. Tautomerization takes place in the solvents pyridine, glacial acetic acid, and in the various derivatives of these. The roles of solvent structure and dynamics on the proton transfer process in these systems are investigated. / Source: Dissertation Abstracts International, Volume: 46-04, Section: B, page: 1188. / Thesis (Ph.D.)--The Florida State University, 1985.