Global and Local Models for Dilution Factors: Theory and Stimulated Emission Pumping Experiments

The dilution factor is a measure of the intramolecular vibrational energy redistribution (IVR) an excited state undergoes. The distribution of dilution factors for a single molecule (SCCl2) was examined. Stimulated emission pumping (SEP) experiments were performed on SCCl2, probing the 7000--8,000 cm-1 range on the ground electronic state from first excited state and the 7,000--10,000+ cm-1 range from the second electronic state. An extended cross correlation analysis was applied to obtain more accurate measurements of dilution factors. Simulated SEP spectra were constructed according to two theoretical models: a globally random Golden Rule model and a locally random analytical model. Autocorrelation of the experimental and simulated differences revealed a simple and robust method of analyzing the distribution of dilution factors within a spectrum.

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

2015

Author dc:creator

• Lee, Sandra

Contributors dc:contributor

• Martin Gruebele

• Chemistry, Physical

Language dc:language

eng

Identifier

(MiAaPQ)AAI3202124

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84214