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This dissertation explores the use of photoelectron imaging spectrometry to probe the molecular electronic structure of various chemical systems, with an emphasis on photoelectron angular distributions. Experimental ion generation, mass selection, laser photodetachment, and photoelectron ion imaging were all done in a photoelectron imaging spectrometer described in detail. Results from simplistic systems, OH- and CH-, are used to illustrate the general and fundamental capabilities of imaging spectroscopy and angular distributions. This illustration is then expanded when both qualitative and quantitative analyses of photoelectron angular distributions are used to aid in the understanding of the electronic structure of several heterocyclic aromatic systems. First a qualitative analysis aids in the exploration of the electronic structure of thiophenide, C₄H₃S⁻, and furanide, C₄H₃O⁻. Ground and excited C₄H₃S and C₄H₃O radical states are observed, and bond dissociation energies are defined. Next, a new model used to qualitatively analyze photoelectron angular distributions resulting from mixed s - p hybrid states is presented and applied to detachment from pyridinide, C₅H₄N⁻; as a benchmark system. Before further exploring this model, the synthesis of several deuterated heterocyclic compounds is presented in order to determine the experimentally produced systems in our experimental setup. The electronic structure of the resultant molecules oxazolide, C₃H₂NO⁻, and thiazolide, C₃H₂NS⁻; are then investigated. Using this new qualitative model, the mixed s - p states model, to evaluate the angular distributions of the systems, the hybridization of the anion molecular orbitals is probed. Comparison of the photoelectron angular distributions that are modeled for each heterocyclic aromatic system yields several trends relating aromatic stabilization, molecular hybridization, and bond dissociation energies. A new qualitative model is then presented to evaluate photoelectron angular distributions resulting from mixed p - d states and applied to detachment from NO⁻. Finally, new ideas and directions are proposed.

The electronic structure and photofragmentation dynamics of several molecular and cluster anions have been investigated in the gas phase via negative ion velocity-map imaging photoelectron spectrometer combined with tandem time-of-flight (TOF) mass spectrometry. Among others, photoelectron imaging investigation of the halogen- and cyano- substituted methyl radicals and corresponding carbenes has been performed on several mono- and hetero- substituted species – dicyanomethyl and chlorocyanomethyl radicals, ·CH(CN)₂ and ·CHClCN, and corresponding carbenes, NCCCN and CClCN. The results are discussed in comparison with the corresponding dichloro- species, focusing on the divergent effects of the halogen and pseudohalogen (CN) substitutions. A cooperative (captodative) interaction of π-donor Cl and π-acceptor cyano groups favors the increased stability of the CHClCN radical, but a competition of the two substituents is observed in the singlet-triplet splitting of the carbene. The experimental results are consistent with high level ab-initio calculations using the spin-flip approach in combination with the coupled-cluster theory. The C-H bond dissociation energies were determined for several substituted methanes and discussed. Additionally, a practical model is presented for describing the energy dependence of laboratory-frame photoelectron angular distributions in direct photodetachment from (in principle) any molecular orbital using linearly polarized light. A transparent mathematical approach is used to generalize the Cooper-Zare central-potential model to initial states of any mixed character. In the limits of atomic photodetachment or photoionization, the model reproduces the Cooper-Zare formula. In the case of electron emission from an orbital described as a superposition of s- and p-type functions, the model yields the previously obtained s-p mixing formula. The formalism is further advanced using the Hanstorp approximation, valid for anion photodetachment only, whereas the relative scaling of the partial wave cross-sections is assumed to follow the Wigner threshold law. The resulting model can be used to describe the energy dependence of photoelectron anisotropy for any atomic, molecular, or cluster anions. As a benchmark case, we compare the predictions of the p-d variant of the model to the experimental results for NO⁻ photodetachment and show that the observed anisotropy trend is described well using physically meaningful values of the model parameters.

The transfer of electrons to and from a molecule is one of the more fundamental and important chemical processes. One such important example is the reduction-oxidation (redox) cycles in catalysts and enzymes. In the hydrogenase enzymes, adding and removing electrons is one of the key processes for generating H₂ from water molecules. Finding a direct free energy relation between the vertical ionization energies (IE(V)) measured spectroscopically by gas-phase photoelectron spectroscopy and the oxidation potentials (E(1/2)) measured thermodynamically in solution by cyclic voltammetry (CV) for molecules is an important aspect for developing effective catalysts. In this study, a series of organometallic compounds such as metallocenes were used for investigating the free energy relationships and catalysts inspired by the active sites of [FeFe]-hydrogenases enzymes were evaluated for their ability to produce H₂ from electrocatalytic reduction of weak acids. The first part of the dissertation explores metallocenes of the form (η⁵-C₅H₅)₂M (M= Fe, Ru, Os, Co, Ni) as the model for developing the free energy relation between gas phase ionization energies (IE(V)) and solution oxidation potentials (E(1/2)). It was found that computing the electronic properties of Cp₂Fe, Cp₂Ru, and Cp₂Os using VWN-Stoll and OPBE density functional theory (DFT) functional was successful with root mean square deviation (RMSD) of 0.02 eV between the experimental and calculated ionization energies. However, calculated ionization energies of Cp₂Co and Cp₂Ni were less successful with RMSD of 0.3 eV between the experimental and calculated ionization energies. Introduction of the B3LYP or M06 hybrid DFT functionals yielded much improved results (0.1 eV) over the previous combinations of DFT functional for Cp2Co and Cp2Ni. The energy relation between the two experimental measurements was established and further computational studies revealed that the solvation energy was the largest energy contribution between IE(V) and E(1/2) in the five studied metallocenes. The RMSD of the calculated oxidation potentials, after adjusting for the error in gas-phase ionization energies, was 0.09 V. The second part of the dissertation explores a series of catalysts inspired by the active sites of [FeFe]-hydrogenase enzymes; μ-(2,3-pyrazinedithiolato)diironhexacarbonyl (PzDT-cat), Fe₂(μ-X₂C₅H₈O)(CO)₆ (where X = S, Se, Te), and Fe₂(μ-1,3-SC₃H₆X)(CO)₆ (where X = Se and Te) for their ability to produce H₂ from weak acids utilizing the computational techniques and knowledge gained from the metallocene study. Even though the overall electronic perturbation from μ-(1,2-benzenedithiolato)diironhexacarbonyl (BDT-cat) to μ-(2,3-pyridinedithiolato)diironhexacarbonyl (PyDT-cat) to PzDT-cat is found to be small, the reduction potential of PzDT-cat was found to be 0.15 V less negative than that of BDT-cat resulting in less energy required for initiating electrocatalytic H₂ production over the BDT-cat and PyDT-cat. Lower reorganization energy has been achieved by substitutions of larger chalcogens at the Fe₂S₂ core. However, the electrocatalytic production of H₂ from acetic acid in acetonitrile was found to be diminished upon going from analogous S to Se to Te species. This is ascribed to the increase in the Fe–Fe bond distance with a corresponding increase in the size of the chalcogen atoms from S to Se to Te, disfavoring the formation of a carbonyl-bridged structure in the anion which is thought to be critical to the mechanism of H₂ production.

Understanding organic semiconductor interfaces is critical to developing organic photovoltaics (OPV). OPV interfaces are disordered due to weak intermolecular interactions, resulting in diverse charge transfer micro-environments. I present experimental data isolating high-order intermolecular interactions controlling interfacial energy level alignment and describe new instrumental capabilities providing access to the local electronic and kinetic landscape at organic semiconductor interfaces. Interface formation between vanadyl naphthalocyanine (VONc) and highly ordered pyrolytic graphite (HOPG) is investigated. Ultraviolet photoemission spectroscopy (UPS) shows that the VONc binding energy (BE) decouples from the work function, shifting in an opposite direction and contradicting the standard interface dipole model. This effect is quantitatively described using an electrostatic depolarization model and confirmed by simulations which show an inhomogeneous potential at the interface. New data and literature values suggest orthogonality between polarizability and molecular dipole in polar porphyrazines. Their potential for interface engineering is discussed. The electron-rich Au(111)/VONc interface is investigated. The organic layer induces a large interface dipole in Au(111) which can be fit to a depolarization model. Ionization potential and depolarization data suggest that the second VONc layer on Au(111) adopts a tilted geometry. Electrostatic differences between Au(111)/VONc and HOPG/VONc are discussed, demonstrating that interface dipole contributions are not interchangeable. The surface states of the Au(111)/VONc interface are characterized by angle resolved 2-photon photoemission to determine the magnitude of the perturbation. The measured free-electron-like effective mass and BE destabilization of the Shockley state is attributed to step edges caused by lifting the Au(111) (22 x √3) reconstruction. The Shockley state is accessible primarily through resonance with the n = 1 image state. Another resonance between the image state and a molecular state of VONc is tentatively identified. Design and construction of a confocal fluorescence microscope capable of single molecule detection in ultrahigh vacuum is described. Initial images and fluorescence trajectories demonstrate the ability to measure charge transfer kinetics between an individual organic semiconductor molecule and well-characterized insulating surfaces. Progress towards completion of a scanning photoionization microscope is presented. The microscope demonstrates diffraction-limited imaging capabilities using fs-laser-generated photoelectron current as contrast. Recommendations are given towards achieving spectral resolution and for future experimental systems.

This thesis investigates the electronic structure of iron phthalocyanine (Fe(II)Pc) andiron phthalocyanine chloride (Fe(III)PcCl) immobilized on surfaces. For this purposetwo different deposition methods are used and compared: smearing the molecularpowder under atmosphere condition and evaporation of a molecular layer inultra-high vacuum. The electronic states of FePc and FePcCl are probed withphotoelectron spectroscopy (PES) and compared in relation to the ionic state of thecentral metal (Fe). The PE spectra show that evaporation of FePcCl at around 350°Cresults in dissociation of the chlorine from the FePc molecule, which is stable at thistemperature. Mass spectroscopic measurements during heating of FePcCl in ultra-highvacuum (UHV) show a clear Cl signal for temperature still below 250°C. Theoreticalcalculations of the binding energy for Cl in FePcCl seem to indicate dissociation of theCl from the molecules.

No description available.

Thin coatings of photoresponsive, pyrimidine-terminated molecules, attached to gold or quartz substrates in contact with water, undego photodimerisation and wettability changes when irradiated with UV light at 280 and 240mm. Spin-casting and chemisorption techniques were used to prepare the thin films. / Thesis (PhDApSc)--University of South Australia, 2000.

Thin coatings of photoresponsive, pyrimidine-terminated molecules, attached to gold or quartz substrates in contact with water, undego photodimerisation and wettability changes when irradiated with UV light at 280 and 240mm. Spin-casting and chemisorption techniques were used to prepare the thin films. / Thesis (PhDApSc)--University of South Australia, 2000.

Thesis (M. Sc.)--University of Adelaide, Dept. of Physics, 1985. / Includes bibliographical references (leaves 76-78).