Development and Application of Embedding Methods for the Simulation of Large Chemical Systems

The high computational cost of correlated wavefunction theory (WFT) calculations has motivated the development of numerous methods to partition the description of large chemical systems into smaller subsystem calculations. For example, WFT-in-DFT embedding methods facilitate the partitioning of a system into two subsystems: a subsystem A that is treated using an accurate WFT method, and a subsystem B that is treated using a more efficient Kohn-Sham density functional theory (KS-DFT) method. Representation of the interactions between subsystems is non-trivial, and often requires the use of approximate kinetic energy functionals or computationally challenging optimized effective potential calculations; however, it has recently been shown that these challenges can be eliminated through the use of a projection operator. This dissertation describes the development and application of embedding methods that enable accurate and efficient calculation of the properties of large chemical systems.

Chapter 1 introduces a method for efficiently performing projection-based WFT-in-DFT embedding calculations on large systems. This is accomplished by using a truncated basis set representation of the subsystem A wavefunction. We show that naive truncation of the basis set associated with subsystem A can lead to large numerical artifacts, and present an approach for systematically controlling these artifacts.

Chapter 2 describes the application of the projection-based embedding method to investigate the oxidative stability of lithium-ion batteries. We study the oxidation potentials of mixtures of ethylene carbonate (EC) and dimethyl carbonate (DMC) by using the projection-based embedding method to calculate the vertical ionization energy (IE) of individual molecules at the CCSD(T) level of theory, while explicitly accounting for the solvent using DFT. Interestingly, we reveal that large contributions to the solvation properties of DMC originate from quadrupolar interactions, resulting in a much larger solvent reorganization energy than that predicted using simple dielectric continuum models. Demonstration that the solvation properties of EC and DMC are governed by fundamentally different intermolecular interactions provides insight into key aspects of lithium-ion batteries, with relevance to electrolyte decomposition processes, solid-electrolyte interphase formation, and the local solvation environment of lithium cations.

Electrical and optical investigations of beta-gallium oxide

An experimental investigation of the optical properties of β–gallium oxide has been carried out, covering the wavelength range 220-2500 nm.

The refractive index and birefringence have been determined to about ± 1% accuracy over the range 270-2500 nm, by the use of a technique based on the occurrence of fringes in the transmission of a thin sample due to multiple internal reflections in the sample (ie., the "channelled spectrum" of the sample.)

The optical absorption coefficient has been determined over the range 220 - 300 nm, which range spans the fundamental absorption edge of β – Ga₂O₃. Two techniques were used in the absorption coefficient determination: measurement of transmission of a thin sample, and measurement of photocurrent from a Schottky barrier formed on the surface of a sample. Absorption coefficient was measured over a range from 10 to greater than 10⁵, to an accuracy of better than ± 20%. The absorption edge was found to be strongly polarization-dependent.

Detailed analyses are presented of all three experimental techniques used. Experimentally determined values of the optical constants are presented in graphical form.