Experimental and theoretical studies of hydrogen -bonded systems: Tropolone and its water-containing clusters together with methanol and water clusters
Abstract
In the first set of experiments, cavity ringdown spectroscopy is combined with laser-induced fluorescence spectroscopy to determine relative single-vibronic level fluorescence quantum yields of jet-cooled tropolone and tropolone-(H 2O)n clusters with n = 1–4 in its S1 state. The complexation of a single water molecule to tropolone is seen to increase the fluorescence quantum yield of tropolone by a factor of 8.0 ± 1.0. As the prototypical alkyl alcohol, methanol's properties provide an important comparison with water, and set a benchmark for the properties of larger alcohols. This second study has as its goal the calculation of the relative binding energies and infrared signatures of a more extensive and representative set of H-bonded methanol cluster structures. The sensitivity of the OH stretch vibrational frequencies and intensities to the hydrogen-bonding environment make the OH stretch infrared spectrum an especially powerful probe of the hydrogen-bonding “architecture” of the clusters. In a third project, an OH stretch-restricted normal coordinate analysis is performed on water octamer cubic clusters and their benzene-containing clusters in order to study the OH stretch vibrational region and predict the spectra for larger clusters.
Degree
Ph.D.
Advisors
Zwier, Purdue University.
Subject Area
Physical chemistry|Chemistry
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