STUDYING LIQUID DYNAMICS WITH OPTICAL KERR EFFECT SPECTROSCOPY

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dc.contributor.advisorFourkas, John Ten_US
dc.contributor.authorHe, Xiaoxiaoen_US
dc.contributor.departmentChemistryen_US
dc.contributor.publisherDigital Repository at the University of Marylanden_US
dc.contributor.publisherUniversity of Maryland (College Park, Md.)en_US
dc.date.accessioned2015-09-18T05:34:19Z
dc.date.available2015-09-18T05:34:19Z
dc.date.issued2015en_US
dc.description.abstractTime-resolved optical Kerr effect (OKE) spectroscopy is an established tech-nique for studying the orientational dynamics of liquids. The reduced spectral density (RSD) obtained from transforming the OKE spectrum into the frequency domain has shown its utility in probing the intermolecular dynamics of liquids. The intermolecular dynamics of benzene and its isotopologues have been inves-tigated using OKE spectroscopy. The observed linear dependence of the collective orientational correlation time on the square root of the moment of inertia leads to the conclusion that there is strong translation-rotation coupling in benzene liquid. By ana-lyzing of the RSDs of benzene and its isotopologues, it is evident that the librational scattering dominates the high-frequency region and plays a major role throughout the RSD. The dynamics of confined liquids have also been studied using OKE spectros-copy. A blue shift of the high-frequency portion of the RSD of confined benzene has been observed. This blue shift is similar to the shift in the RSD of bulk benzene as the temperature is decreased. It is believed that this shift in the high-frequency portion of the RSD reflects the densification of the liquid in confinement. This phenomenon has also been observed in confined pyridine and acetonitrile liquids. OKE spectroscopy has also been employed in studies of the dynamics of nano-confined propionitrile and trimethyl acetonitrile. The results of these studies indicate that propionitrile can form a lipid-bilayer-like structure at the confining surfaces, with the alkyl tails of the sublayers being entangled. However, due to the steric effects im-posed by the tert-butyl group in trimethyl acetonitrile, bilayers are not formed at the confining surfaces for this liquid.en_US
dc.identifierhttps://doi.org/10.13016/M22W6H
dc.identifier.urihttp://hdl.handle.net/1903/16908
dc.language.isoenen_US
dc.subject.pqcontrolledChemistryen_US
dc.subject.pqcontrolledPhysical chemistryen_US
dc.subject.pquncontrolledbenzeneen_US
dc.subject.pquncontrolledinteraction-induced scatteringen_US
dc.subject.pquncontrolledliquid dynamicsen_US
dc.subject.pquncontrollednanoconfined liquiden_US
dc.subject.pquncontrolledOKE spectroscopyen_US
dc.subject.pquncontrolledreduced spectral densityen_US
dc.titleSTUDYING LIQUID DYNAMICS WITH OPTICAL KERR EFFECT SPECTROSCOPYen_US
dc.typeDissertationen_US

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