Density functional theory calculations in materials science and catalysis




Chai, Wenrui

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As scientists are pushing the limit of technology, experimental trial and error explorations are becoming increasingly unaffordable, especially when accurate manipulation of materials at the atomic level is essential. The need for theoretical oversight is ever increasing while traditional empirical theories are becoming obsolete. Density Functional Theory (DFT) is therefore developed as a portable theoretical tool that can shed light on many different fields based on first principle quantum mechanics. It is enjoying increasing popularity for its ability to provide information complementary to experimental characterization methods, as well as its astounding prediction power that can potentially vastly increases experimental output. In this dissertation, I showcase how DFT can be used to support experimental endeavors by providing insights and validations otherwise unobtainable and deepen our understanding of a variety of subjects. DFT calculations are also used to validate and explain experimental characterization results. For isolated Pt atom and Pt clusters with few atoms, the Pt dband center and hydrogen binding energy were calculated, used in conjunction with cyclicvoltammetry data to characterize the Pt atom/clusters and explain the observed activity towards hydrogen evolution reaction. For methodology development, DFT calculations are used to provide a plausible mechanism for the technique of hydrogen elimination monitoring in ultraviolet photodissociation of proteins for mass-spectroscopy to solve protein structures. It shows that depending on the degree of hydrogen bonding engagement, backbone cleavage can take place first and prevent succeeding hydrogen transfer. The results explained why the technique is a reliable method for finding protein structure information. Towards the development of materials, DFT calculations are used to find reaction mechanisms for hydrogenation using carbon-nitrogen-phosphorous pincer Fe catalysts and to find causes for geometry change for post-synthetically modified metal-organic frameworks



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