<p> Radical species are essential in modern chemistry. In addition to fundamental chemistry, their unique chemical bonding and distinct physicochemical features serve critical functions in materials science in the form of organic electronics. Due to their high reactivity, radicals of the main group element are often transient. In recent years, remarkably stable radicals are often stabilized by π-delocalization, sterically demanding side groups, carbenes, and weakly coordinating anions. The impacts of modifications such as electron-donating, electron-withdrawing, and end-capping on the spin density distribution and thermodynamic and kinetic stability of archetypal radical-driven processes such as dimerization are not well understood. This dissertation aims to track the perturbation of spin density from EDG and EWG modifications, provide mechanistic insight into the radical-initiated reactions of conjugated radical cations, and establish correlations between molecular design and thermochemical properties and their resulting kinetic stability by computationally evaluating these characteristics against experimental data. The disclosed connections give useful new recommendations for the rational design of thermodynamically and kinetically stable novel materials.</p>

<p>Fibre suspensions in the fluid medium are common in industry, biology, and the environment. Industrial examples of concentrated suspensions include fresh concrete, uncured solid rocket fuel, and biomass slurries; natural examples include silt transfer in rivers and red blood cells in the blood.  These suspensions often include a Newtonian fluid as their suspending medium; still, these suspensions exhibit a plethora of non-Newtonian properties, such as yield stresses, rate-dependent rheology, and normal stresses, to name a few. Other than volume fraction, the type of fiber material, the presence of fluid-fiber or fiber-fiber interactions such as hydrodynamic, Brownian, colloidal, frictional, chemical, and/or electrostatic determine the rheological behavior of suspension. The average inter-fiber gaps between the neighboring fibers decrease significantly as the suspension volume fraction move towards a concentrated regime. As a result, in this regime, inter-fiber interactions become dominant.  Moreover, the surface asperities are present on the fiber surface even in the case of so-called smooth fibers, as fibers in real suspensions are not perfectly smooth. Hence, contact forces arising from the direct touching of the fibers become one of the essential factors in determining the rheology of suspensions.</p> <p>We first describe the causes of yield stress, shear thinning, and normal stress differences in fibre suspensions. We model the fibers as inextensible continuous flexible slender bodies with the Euler-Bernoulli beam equation governing their dynamics suspended in an incompressible Newtonian fluid. The fiber dynamics and fluid flow coupling is achieved using the immersed boundary method (IBM). In addition, the fiber surface roughness lead to inter-fiber contacts resulting in normal and tangential forces between the fibers, which follow Coulomb’s law of<br> friction. The surface roughness is modeled as hemispherical protrusions on the fiber surfaces. In addition to the comparison of the computational model to the experimental results, we demonstrate that attractive interactions lead to yield stress and shear thinning rheology.</p> <p>Furthermore, we investigate the effects of fiber aspect ratio, roughness, flexibility, and volume fraction on the rheology of concentrated suspensions. We find that the suspension viscosity increases with increasing the volume fraction, roughness, fiber rigidity, and aspect ratio. The increase in relative viscosity is the macroscopic manifestation of a similar increase  in the microscopic contact contribution with these parameters. In addition, we observe positive and negative first and second normal stress differences, respectively, in agreement with previous experiments. Lastly, we propose a modified Maron-Pierce law to quantify the the jamming volume fraction with varying fiber aspect ratio and roughness. Additionally, we provide a constitutive model to calculate the viscosity at various volume fractions, aspect ratios, and shear rates.</p>

<p>This dissertation describes how the surface chemistries of 2D nanomaterials can be modified to alter overall material properties. Specifically, through a focus of the ligand-surface atom bonding in addition to the overall ligand structure we highlight the ability to direct morphological outcomes in lead free halide perovskites, maximize optoelectronic responses in substoichiometric tungsten oxide, and alter physicochemical properties titanium carbide MXenes.   </p>