Title page for ETD etd-12042007-002035
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Type of Document Dissertation
Author Alvarez-Valtierra, Leonardo
URN etd-12042007-002035
Title MOLECULAR EXCITED STATE DYNAMICS VIA HIGH RESOLUTION ELECTRONIC SPECTROSCOPY IN THE GAS PHASE
Degree Doctor of Philosophy
Program Chemistry
School School of Arts and Sciences
Advisory Committee
Advisor Name Title
David W. Pratt Committee Chair
David H. Waldeck Committee Member
David N. Beratan Committee Member
Paul E. Floreancig Committee Member
Keywords
  • acenaphthene
  • methylanisole
  • dihydrophenanthrene
  • methyl internal rotation
  • methylpyrimidine
  • electronic transition
  • excited state
  • intersystem crossing
  • rotationally resolved
  • dibenzothiophene
  • naproxen
  • tunneling splitting
Date of Defense 2007-09-28
Availability unrestricted
Abstract
Dynamical processes can be studied using the high resolution spectroscopy technique. Often, the connection between dynamics and spectroscopy is the uncertainty principle ΔEΔt ≈ ħ; in other cases, dynamics makes its appearance via extra rovibronic peaks, tunneling splittings, anomalous line intensities, and anomalous line broadenings. Among others, these particular spectral details are related to crucial dynamical information occurring in the molecules upon excitation. Through this work, the electronic origin and some vibronic transitions have been investigated where such phenomena are manifested. Consequently, dynamical analyses are performed to explain the apparent unique characteristics present in their experimental spectra.

The molecules studied here include 2-methoxynaphthalene, S-(+)- and R-(-)- naproxen, acenaphthene, acenaphthene-argon complex, 9,10-dihydrophenanthrene, 2-methylanisole, 3-methylanisole, 2-methylpyrimidine, 5-methylpyrimidine, dibenzothiophene, 2,5-diphenylfuran, and 2,5-diphenyl-1,3,4-oxadiazole. The results of the present work lead to interesting insights into the vibrational inversion motion, the hindered methyl group torsional motion, and some dynamical relaxation processes of selected molecules studied. In the case of naproxen, the results obtained to date shed light on the origins of optical activity.

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