Probing solute-solvent interactions: A study of benzene-small moleculevan der Waals complexes
Abstract
The spectroscopy and photophysics of the S$\sb0$-S$\sb1$ transition in several important benzene containing van der Waals' complexes has been investigated using laser induced flourescence (LIF) and resonant enhanced multiphoton ionization (REMPI) techniques. The complexes studied include C$\sb6$H$\sb6$-CCl$\sb4$,-HCl, -H$\sb2$O, -(H$\sb2$O)$\sb2$, C$\sb6$H$\sb5$CH$\sb3$-HCl, and many of the isotopomers. These complexes serve as model systems for the study of solvation effects on the benzene chromophore. The use of the above techniques has allowed the determination of such characteristics of the van der Waals' complexes as binding energy, ionization potential, center of mass separation, van der Waals' vibrational frequencies, and S$\sb1$ lifetimes. The use of the chosen solvents has revealed the importance of charge transfer (C$\sb6$H$\sb6$-CCl$\sb4$) and proton transfer (C$\sb6$H$\sb6$-HCl) interactions in the photophysics of these weakly bound complexes. Also presented is evidence at the molecular level of solute/solvent immiscibility in C$\sb6$H$\sb6$-(H$\sb2$O)$\sb{\rm n}$. The importance of small, model systems in providing a detailed molecular level understanding of bulk phase processes is emphasized.
Degree
Ph.D.
Advisors
Zwier, Purdue University.
Subject Area
Chemistry|Molecules
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