Electronic Structure Theory and Computations: Application of Density Functional Theory to Heterogeneous Catalysis and Density Functional Development

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Electronic Structure Theory and Computations: Application of Density Functional Theory to Heterogeneous Catalysis and Density Functional Development

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2022-12

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Density functional theory (DFT) is the most widely used electronic structure method in quantum chemistry, and it has been used for many applications in physics, biology, and materials. The quality of exchange-correlation functionals is the key determinant of DFT accuracy. Applying DFT to materials and molecules and improving DFT functionals are major areas of activity in quantum chemistry that constitute the focus of this thesis. This thesis reports the application of DFT to heterogeneous catalysis, studies of the performance of various existing functionals, and the development of a new exchange-correlation functional designed for broad accuracy on chemical structures and energies.One of my studies is to evaluate the performance of long-range-corrected (LC) hybrid functionals for calculating vertical ionization energies and to study their performance for the satisfaction of the ionization potential theorem. This kind of functional is useful in calculating fundamental gaps and excitation energies. We found that Minnesota LC-hybrid meta functionals perform quite well in these tests. Catalysis plays an important role in chemical industries. Another focus of this thesis is the application of DFT to heterogeneous catalysis, which is a key kind of process in the movement to a sustainable energy future by increasing energy efficiency and diminishing the accompanying pollution. Two kinds of catalytic reactions with different materials used as catalysts are studied in this work: (i) the reduction of Cu(II) to Cu(0) by residual formate on a metal-organic framework support, in particular NU-1000, and (ii) the semihydrogenation of acetylene to ethylene on bimetallic metal surfaces, in particular Pd/Cu(111). This work determines the most favorable reaction mechanism of Cu(II) reduction on NU-1000, and it successfully explain the changes in activity and selectivity of semihydrogenation on different metal surfaces. To provide an efficient functional with a balance of accuracy and cost to study a broad range of chemical properties and energies, a new exchange-correlation functional called M11plusNX is developed. This functional is built on the previous functional called M11plus, and it has rung-3.5 nonlocal correlation with no Hartree-Fock (HF) exchange. The M11plusNX functional is optimized against a database containing a broad range of chemical energies and properties, and its performance is in the top two of nine examined functionals that have no HF exchange.

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University of Minnesota Ph.D. dissertation. December 2022. Major: Chemistry. Advisor: Donald Truhlar. 1 computer file (PDF); xi, 152 pages.

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Kanchanakungwankul, Siriluk. (2022). Electronic Structure Theory and Computations: Application of Density Functional Theory to Heterogeneous Catalysis and Density Functional Development. Retrieved from the University Digital Conservancy, https://hdl.handle.net/11299/260644.

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