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- Genre: Doctoral Dissertation
Description
Broadband dielectric spectroscopy is a powerful technique for understanding the dynamics in supercooled liquids. It generates information about the timescale of the orientational motions of molecular dipoles within the liquid. However, dynamics of liquids measured in the non-linear response regime has recently become an area of significant interest, because additional information can be obtained compared with linear response measurements.
The first part of this thesis describes nonlinear dielectric relaxation experiments performed on various molecular glass forming-liquids, with an emphasis on the response at high frequencies (excess wing). A significant nonlinear dielectric effect (NDE) was found to persist in these modes, and the magnitude of this NDE traces the temperature dependence of the activation energy. A time resolved measurement technique monitoring the dielectric loss revealed that for the steady state NDE to develop it would take a very large number of high amplitude alternating current (ac) field cycles. High frequency modes were found to be ‘slaved’ to the average structural relaxation time, contrary to the standard picture of heterogeneity. Nonlinear measurements were also performed on the Johari-Goldstein β-relaxation process. High ac fields were found to modify the amplitudes of these secondary modes. The nonlinear features of this secondary process are reminiscent of those found for the excess wing regime, suggesting that these two contributions to dynamics have common origins.
The second part of this thesis describes the nonlinear effects observed from the application of high direct current (dc) bias fields superposed with a small amplitude sinusoidal ac field. For several molecular glass formers, the application of a dc field was found to slow down the system via reduction in configurational entropy (Adam-Gibbs relation). Time resolved measurements indicated that the rise of the non-linear effect is slower than its decay, as observed in the electro-optical Kerr effect. A model was discussed which quantitatively captures the observed magnitudes and time dependencies of the NDE. Asymmetry in these rise and decay times was demonstrated as a consequence of the quadratic field dependence of the entropy change. It was demonstrated that the high bias field modifies the polarization response to the field, even including the zero field limit.
The first part of this thesis describes nonlinear dielectric relaxation experiments performed on various molecular glass forming-liquids, with an emphasis on the response at high frequencies (excess wing). A significant nonlinear dielectric effect (NDE) was found to persist in these modes, and the magnitude of this NDE traces the temperature dependence of the activation energy. A time resolved measurement technique monitoring the dielectric loss revealed that for the steady state NDE to develop it would take a very large number of high amplitude alternating current (ac) field cycles. High frequency modes were found to be ‘slaved’ to the average structural relaxation time, contrary to the standard picture of heterogeneity. Nonlinear measurements were also performed on the Johari-Goldstein β-relaxation process. High ac fields were found to modify the amplitudes of these secondary modes. The nonlinear features of this secondary process are reminiscent of those found for the excess wing regime, suggesting that these two contributions to dynamics have common origins.
The second part of this thesis describes the nonlinear effects observed from the application of high direct current (dc) bias fields superposed with a small amplitude sinusoidal ac field. For several molecular glass formers, the application of a dc field was found to slow down the system via reduction in configurational entropy (Adam-Gibbs relation). Time resolved measurements indicated that the rise of the non-linear effect is slower than its decay, as observed in the electro-optical Kerr effect. A model was discussed which quantitatively captures the observed magnitudes and time dependencies of the NDE. Asymmetry in these rise and decay times was demonstrated as a consequence of the quadratic field dependence of the entropy change. It was demonstrated that the high bias field modifies the polarization response to the field, even including the zero field limit.
ContributorsSamanta, Subarna (Author) / Richert, Ranko (Thesis advisor) / Steimle, Timothy (Committee member) / Wolf, George H. (Committee member) / Arizona State University (Publisher)
Created2016
Description
Transition metal oxides are used for numerous applications, includingsemiconductors, batteries, solar cells, catalysis, magnetic devices, and are commonly
observed in interstellar media. However, the atomic-scale properties which dictate the
overall bulk material activity is still lacking fundamental details. Most importantly, how
the electron shells of metals and O atoms mix is inherently significant to reactivity. This
thesis compares the binding and excited state properties of highly correlated first-row
transition metal oxides using four separate transition metal systems of Ti, Cr, Fe and Ni.
Laser ablation coupled with femtosecond pump-probe spectroscopy is utilized to resolve
the time-dependent excited state relaxation dynamics of atomically precise neutral
clusters following 400 nm (3.1 eV) photoexcitation. All transition metal oxides form
unique stable stoichiometries with excited state dynamics that evolve due to oxidation,
size, or geometry. Theoretical calculations assist in experimental analysis, showing
correlations between charge transfer characteristics, electron and hole localization, and
magnetic properties to the experimentally determined excited state lifetimes.
This thesis finds that neutral Ti and Cr form stable stoichiometries of MO2 (M =
Ti, Cr) which easily lose up to two O atoms, while neutral Fe and Ni primarily form MO
(M = Fe, Ni) geometries with suboxides also produced. TiO2 clusters possess excited
state lifetimes that increase with additional cluster units to ~600 fs, owing to a larger
delocalization of excited charge carriers with cluster size. CrO2 clusters show a unique
inversed metallic behavior with O content, where the fast (~30 fs) metallic relaxation
component associated with electron scattering increases with higher O content, connected
to the percent of ligand-to-metal charge transfer (LMCT) character and higher density of
states. FeO clusters show a decreased lifetime with size, reaching a plateau of ~150 fs at
the size of (FeO)5 related to the density of states as clusters form 3D geometries. Finally,
neutral (NiO)n clusters all have similar fast lifetimes (~110 fs), with suboxides possessing
unexpected electronic transitions involving s-orbitals, increasing excited state lifetimes
up to 80% and causing long-lived states lasting over 2.5 ps. Similarities are drawn
between each cluster system, providing valuable information about each metal oxide
species and the evolution of excited state dynamics as a result of the occupied d-shell.
The work presented within this thesis will lead to novel materials of increased reactivity
while facilitating a deeper fundamental understanding on the effect of electron
interactions on chemical properties.
ContributorsGarcia, Jacob M. (Author) / Sayres, Scott G (Thesis advisor) / Yarger, Jeffery (Committee member) / Steimle, Timothy (Committee member) / Arizona State University (Publisher)
Created2021