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- All Subjects: Dielectric relaxation
- All Subjects: Noise models
- Creators: Wolf, George
Description
A driving force for studies of water, alcohols, and amides is the determination of the role of hydrogen bonding. Hydrogen bonds can break and reform, consequently creating supramolecular structures. Understanding the role supramolecular structures play in the dynamics of monohydroxyl alcohols is important to understanding hydrogen bonding in more complex systems such as proteins. Since many monohydroxyl alcohols are good glass formers, dielectric spectroscopy in the supercooled regime is used to gather information about the dynamics of these liquids. Application of high external fields will reversibly alter the polarization responses of the material from the linear response. This results in nonlinear dielectric effects (NDE) such as field induced suppression (saturation) and enhancement of amplitudes (chemical effects) as well as shifts in the time constants toward slower (entropy) and faster (energy absorption) dynamics.
The first part of this thesis describes the nonlinear dielectric experiments on monohydroxyl alcohols, with an emphasis on the time dependence of NDEs. For the first time, time-dependent experiments on monoalcohols were done, the results showed that NDEs occur on the Debye time scale. Furthermore, physical vapor deposition (PVD) is used to modify the supramolecular structure of 4-methyl-3-heptanol. Upon deposition the film cannot form the ring like structures, which are preferred in the bulk material. The as deposited film shows an enhancement of the dielectric peak by a factor of approximately 11 when compared to the bulk material. The conversion from the as deposited material back to the near bulk material was found to occur on the Debye timescale.
The second part of this thesis focuses on the question of what is governing the field induced changes seen in the liquids studied. Here a complete set of high field experiments on highly polar propylene carbonate derivatives were performed. It was demonstrated that these materials exhibit a Debye-like peak and using a combination of Adam-Gibbs and Fröhlich’s definition of entropy, proposed by Johari [G.P. Johari, J. Chem. Phys 138, 154503 (2013)], cannot solely be used to describe a frustration of dynamics. It is important to note that although these material exhibit a Debye like peak, the behavior is much different than monoalcohols.
The first part of this thesis describes the nonlinear dielectric experiments on monohydroxyl alcohols, with an emphasis on the time dependence of NDEs. For the first time, time-dependent experiments on monoalcohols were done, the results showed that NDEs occur on the Debye time scale. Furthermore, physical vapor deposition (PVD) is used to modify the supramolecular structure of 4-methyl-3-heptanol. Upon deposition the film cannot form the ring like structures, which are preferred in the bulk material. The as deposited film shows an enhancement of the dielectric peak by a factor of approximately 11 when compared to the bulk material. The conversion from the as deposited material back to the near bulk material was found to occur on the Debye timescale.
The second part of this thesis focuses on the question of what is governing the field induced changes seen in the liquids studied. Here a complete set of high field experiments on highly polar propylene carbonate derivatives were performed. It was demonstrated that these materials exhibit a Debye-like peak and using a combination of Adam-Gibbs and Fröhlich’s definition of entropy, proposed by Johari [G.P. Johari, J. Chem. Phys 138, 154503 (2013)], cannot solely be used to describe a frustration of dynamics. It is important to note that although these material exhibit a Debye like peak, the behavior is much different than monoalcohols.
ContributorsYoung-Gonzales, Amanda R (Author) / Richert, Ranko (Thesis advisor) / Angell, Charles (Committee member) / Wolf, George (Committee member) / Arizona State University (Publisher)
Created2019
Description
Fluctuations with a power spectral density depending on frequency as $1/f^\alpha$ ($0<\alpha<2$) are found in a wide class of systems. The number of systems exhibiting $1/f$ noise means it has far-reaching practical implications; it also suggests a possibly universal explanation, or at least a set of shared properties. Given this diversity, there are numerous models of $1/f$ noise. In this dissertation, I summarize my research into models based on linking the characteristic times of fluctuations of a quantity to its multiplicity of states. With this condition satisfied, I show that a quantity will undergo $1/f$ fluctuations and exhibit associated properties, such as slow dynamics, divergence of time scales, and ergodicity breaking. I propose that multiplicity-dependent characteristic times come about when a system shares a constant, maximized amount of entropy with a finite bath. This may be the case when systems are imperfectly coupled to their thermal environment and the exchange of conserved quantities is mediated through their local environment. To demonstrate the effects of multiplicity-dependent characteristic times, I present numerical simulations of two models. The first consists of non-interacting spins in $0$-field coupled to an explicit finite bath. This model has the advantage of being degenerate, so that its multiplicity alone determines the dynamics. Fluctuations of the alignment of this model will be compared to voltage fluctuations across a mesoscopic metal-insulator-metal junction. The second model consists of classical, interacting Heisenberg spins with a dynamic constraint that slows fluctuations according to the multiplicity of the system's alignment. Fluctuations in one component of the alignment will be compared to the flux noise in superconducting quantum interference devices (SQUIDs). Finally, I will compare both of these models to each other and some of the most popular models of $1/f$ noise, including those based on a superposition of exponential relaxation processes and those based on power law renewal processes.
ContributorsDavis, Bryce F (Author) / Chamberlin, Ralph V (Thesis advisor) / Mauskopf, Philip (Committee member) / Wolf, George (Committee member) / Beckstein, Oliver (Committee member) / Arizona State University (Publisher)
Created2018