Infrared Laser Excitation and Fluorescence Spectra: A Study of Intramolecular Vibrational Energy Relaxation

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.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Stewart, George Michael

• Chemistry, Physical

Identifier

(UMI)AAI8324648

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70228