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Full-Text Articles in Physical Sciences and Mathematics
Novel Nonresonant And Resonant Mechanisms Leading To The Breakdown Of The Franck-Condon Approximation In Photoionization, David Adam Hardy
Novel Nonresonant And Resonant Mechanisms Leading To The Breakdown Of The Franck-Condon Approximation In Photoionization, David Adam Hardy
LSU Doctoral Dissertations
This thesis attempts to answer the question of how electrons interact with a molecular framework prior to and during emission through photoionization. These studies interrogate several behaviors of allowed and forbidden photoelectron transitions such as shape resonances, non-resonant intrachannel vibronic coupling as a result of Cooper minima, and chemically-induced nonresonant coupling, all of which provide new insights into correlations between the electronic and molecular degrees of freedom. Research presented in this thesis utilizes high-resolution photoelectron spectroscopy, and undulator-based synchrotron radiation at the Advanced Light Source, a synchrotron radiation source in Berkeley, California. Data are collected from near threshold to several …
Studies On A Dirhodium Tetraphosphine Hydroformylation Catalyst, Darina Polakova
Studies On A Dirhodium Tetraphosphine Hydroformylation Catalyst, Darina Polakova
LSU Doctoral Dissertations
The dirhodium tetraphosphine catalyst [Rh2(nbd)2(rac-et,ph-P4)](BF4)2 was investigated in acetone and water/acetone in order to explain better hydroformylation results in the latter solvent. In-situ NMR spectroscopy showed slower degradation in water/acetone. Less tendency to form penta/hexacarbonyl complexes in water/acetone was shown by 31P{1H} NMR and FT-IR. A pH decrease and hydroformylation studies in presence of a base indicated formation of a monocationic monohydride species. A new reaction mechanism was suggested that takes into account the observed differences from the acetone solvent system. The presence of water enabled production of hydride species when the dirhodium catalyst was exposed to CO gas. We …