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Photovoltaic (PV) technologies are a promising approach to achieve clean, renewable energy production on a global scale. However, the widespread implementation of this technology is limited due to the intricate challenges associated with its complex electrochemical processes. One such challenge is the formation of long-lived charge-separated states (CSSs), a process that directly influences device efficiencies. Viable strategies for increasing CSS lifetimes involve the inhibition of parasitic back-electron transfer pathways. In liquid-junction PVs, electronic recombination is prevented by utilizing redox electrolytes that promote directional electron transfer at the electrode/electrolyte interface, where forward electron transfer (i.e. to the electrode) is favored and the corresponding electronic recombination reaction is impeded. To meet this criterion, researchers seek to employ redox electrolytes that undergo a spin-exchange reaction induced by electron transfer. This event, known as charge transfer-induced spin crossover (CTISC), significantly increases the reorganization energy associated with electronic recombination, producing long-lived CSSs and elevated device efficiency. This dissertation describes a suite of manganese-based redox mediators that exhibit CTISC across a tunable range (1.5 V) of formal potentials (E1/2). These complexes are utilized as redox electrolytes in liquid-junction PVs and result in a two-fold enhancement in the device efficiency relative to other CTISC redox species. Photosensitizer regeneration rates are monitored using transient absorption spectroscopy (TAS) to discern the optimal E1/2 values in this class of complexes while density functional theory is employed to calculate the reorganization energy of each species. By implementing these promising electrolytes into PV devices, scientists and engineers are armed with new tools to increase the accessibility and efficiency of next-generation PVs, thereby transforming past promises into progress. / Doctor of Philosophy / To realize next-generation renewable fuels, scientists must understand how electron transfer at an interface is controlled. This dissertation highlights one method of forming a chemically useful and long-lived charge separated state. The formation of this charge separated state is achieved through an electronic reorganization that occurs at a metal center after electron transfer. Chapters 2, 3, and 4 investigate the synthesis and characterization of new metal species that possess this electronic reorganization process and provide an advanced understanding of how this process facilitates the formation of long-lived charge separated states. This work is intended to motivate new schools of thought that aid the design of next-generation catalytic materials for light-driven chemical reactions.

When scattering intensity is plotted against the dimensionless quantity qR, where q is the magnitude of the scattering wave vector and R is the radius of the particle, in log-log scale the scattering curve shows a power-law structure which defines characteristic crossovers. This work reveals some new relationships between the power-law structure and the particle properties. In this work, computer simulation results from T-matrix, Mie theory, and discrete dipole approximation methods are used to study the far field intensity and the internal field of the particles. Scattering by both weakly and strongly refractive particles are studied. For weakly refractive randomly oriented spheroidal particles, how the phasor cancellation-based tip volume method can be applied to predict the scattering envelope is demonstrated. The relationship between backscattering enhancement and the curvature of the weakly refractive particles is explained. In strongly-refractive particles when the phase shift parameter is high, regions with higher field amplitudes start to appear. These regions are recognized as the hot spot regions. In this work, a proper definition is given to the hot spot region. The relationships between the hot spot region and the power-law structure, between the hot spot region and the particle morphology, and between the power-law structure and the particle morphology are extensively studied for scattering by spherical particles. A new semi-quantitative phasor analysis method is introduced, and the new method is used with color-coded phasor plots to identify how different regions of the particle contribute to the scattering pattern to get an insight into the physics behind the scattering. How different regions of the particle contribute to the second crossover (SC) and the backscattering enhancement is presented. Relationships between the SC, particle size, and relative refractive index of the particle are derived. It was identified that the scattering angle at the SC depends only on the relative refractive index of the particle. How the findings of this work can be applied to solve the inverse electromagnetic scattering problem for a single non-absorbing spherical particle is also discussed.

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