Title page for ETD etd-1114102-161158

Type of Document Dissertation
Author Rathbone, Gerald Jeffery
Author's Email Address grathb1@lsu.edu
URN etd-1114102-161158
Title Mode Specific Photoionization Dynamics in Polyatomic Molecules
Degree Doctor of Philosophy (Ph.D.)
Department Chemistry
Advisory Committee
Advisor Name Title
Erwin D Poliakoff Committee Chair
Neil Kestner Committee Member
Randal Hall Committee Member
Roger Staukbauer Committee Member
Karsten Thompson Dean's Representative
  • photoionization dynamics
Date of Defense 2002-10-29
Availability unrestricted
The work presented in this dissertation presents new work on polyatomic photoionization. In these investigations, the broad range behavior of both allowed and forbidden vibrational modes in linear triatomic systems were studied to understand mode specific aspects of photoionization. The current study is made possible by the experimental strategy of exploiting high resolution photoelectron spectroscopy and the high brightness of third generation synchrotron radiation sources. The data is taken typically tens of eVs past the ionization potential. The strategy that I employ is to probe alternative vibrational modes which are frequently affected differently following resonant ionization. Such vibrationally resolved data can be used to understand how the correlation between vibration and electron energy reveals microscopic insights into the photoelectron scattering process. Moreover, the mode specific behavior contains a wealth of information not only regarding allowed transitions, but also contains information on how forbidden transitions gain surprising amounts of intensity. A previously overlooked mechanism for the appearance of forbidden nontotally symmetric vibrations was discovered resonantly amplified vibronic symmetry breaking. The photoelectron the culprit for the symmetry breaking which induces the excitation of nominally forbidden vibrational excitations. In a more general sense, these results will demonstrate that some fundamental spectroscopic approximations are not always valid, and can lead to surprising consequences.
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