Biogenic secondary organic aerosol (SOA) particles, produced by forest ecosystems across the globe, are principal, yet poorly understood constituents in the climate system. These atmospheric particles form when biogenic volatile organic compounds (BVOCs) react with atmospheric oxidants, leading to increasingly lower volatility oxidation products that partition into the condensed phase...
This thesis describes a series of fundamental studies that address the role of electrostatic interactions in modulating i) the permeability of the ligand shell of a colloidal quantum dot (QD) to an anionic redox probe; ii) the resulting yield of photoinduced electron exchange within the QD ‒ redox probe complex;...
The development and use of organic anionic chromophores that absorb the entire visible spectrum & into the near-infrared region while providing highly reducing equivalents is pinnacle for artificial photosynthesis. This dissertation investigates the rational design of new donor-acceptor systems for artificial photosynthesis that couple naphthalene diimide (NDI)/perylene diimide (PDI) radical...
In solar energy conversion ranging from artificial photosynthesis to photocatalysis, transition metal complexes (TMC) are essential building blocks due to several attractive properties: intense absorption within the solar spectrum, presence of charge-transfer excited state, and substrate binding capability through coordination geometry changes. In order to gain insight into controlling solar...
Increasing industrialization and the resulting negative environmental impacts highlight the need to develop alternative renewable energy sources. The Sun is a massive source and organic solar cells are a growing field of study. As new materials are synthesized, the efficiencies of organic solar cells continue to grow, but without an...
Organic semiconductors have shown great promise for optoelectronic applications, particularly solar photovoltaics. Critical to their success is the ability to understand and manipulate the relationship between molecular structure and bulk properties. Substantial progress on understanding structural influences on electronic properties has been made for the conjugated polymers and small molecules...
Electrochemical reactions on the nanoscale play a pivotal role in a variety of areas, including electrocatalysis, energy conversion and storage, corrosion prevention, plasmon driven chemistry, and so forth. An in-depth knowledge of how site-specific compositions and morphologies locally affect the electron transfer kinetics will greatly benefit the design of catalysts,...
Numerous photophysical processes in both natural and artificial systems are dictated by the interaction between chromophores. For example, in photosynthesis, light is absorbed by an antenna complex composed of an array of chlorophyll chromophores that collectively transfer the energy to the reaction center where interactions between a series of redox...
Surface-enhanced Raman spectroscopy (SERS) is a powerful analytical technique that can detect single molecules and simultaneously obtain structural information. When an analyte molecule binds to a nanostructured noble metal surface, the otherwise weak normal Raman signal is enhanced by as much as a factor of 108. This makes SERS the...
In this thesis, I present the development and benchmarking of several theoretical methods designed to enable the rigorous modeling of magnetic properties of molecules containing one or a few heavy atoms, particularly single-molecule magnets. The new methods use a full four-component treatment of relativity, allowing spin–orbit effects to be taken...