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Title:Infrared Laser Excitation and Fluorescence Spectra: A Study of Intramolecular Vibrational Energy Relaxation
Author(s):Stewart, George Michael
Department / Program:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(s):Chemistry, Physical
Abstract:Infrared fluorescence measurements have been used to determine the presence or absence of intramolecular vibrational relaxation (or more precisely state mixing) from an excited C-H stretch in twenty three representative molecules varying in size from methane to norbornene. Included are aliphatic hydrocarbons, aromatic molecules, ethers, and ketones, including cyclic molecules. The rate of resonance fluorescence, calculated relative to a non-relaxing molecule was used as the criterion of relaxation. Small rates imply state mixing and hence in the large molecule limit, relaxation. The primary correlation with the presence of mixing is with state density; about 10 states per wavenumber (cm('-1)) are needed to insure mixing. The spread in threshold densities reflects variations in anharmonicity. For some molecules true relaxed (non C-H stretch) fluorescence is observed.
These experiments were done in a molecular beam, using a pulsed optical parametric oscillator for excitation and a circular variable filter for spectral resolution.
Issue Date:1983
Description:83 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1983.
Other Identifier(s):(UMI)AAI8324648
Date Available in IDEALS:2014-12-15
Date Deposited:1983

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