Houck, Shannon Elizabeth2022-12-302022-12-302021-07-07vt_gsexam:31127http://hdl.handle.net/10919/113001Over the past few decades, single-molecule magnets (SMMs) have been an area of significant interest due to their plethora of potential uses, including possible applications to quantum computing and compact data storage devices. Although theoretical chemistry calculations could aid our understanding of the magnetic couplings present in these types of systems, they are often multiconfigurational in nature, making them difficult to model with tradi- tional single-reference approaches. Methods to handle these types of strongly correlated systems have been developed but often have significant drawbacks, and so these molecules remain difficult to model computationally. In this work, we discuss the application of Fock-space CI approaches to large transition metal complexes. First, we introduce a novel formalism which combines the spin-flip (SF), ioniza- tion potential (IP), and electron affinity (EA) approaches. This redox spin-flip approach, the restricted active space spin-flip and ionization potential/electron affinity (RAS-SF-IP/EA) method, is applied to several molecules exhibiting double exchange behavior. Model Hamil- tonian parameters are extracted from energy gaps and found to be in qualitative agreement with experiment. Having shown the efficacy of this approach, we move on to optimization, using a diagrammatic approach to derive equations for several RAS-1SF-IP/EA schemes. These equations allow direct construction of the most expensive intermediates in the David- son algorithm and should provide significant speedup, allowing application of Fock-space CI approaches to larger systems than ever before. The derived equations are implemented in the LibRASSF package in Q-Chem, as well as in an open-source PyFockCI code, avail- able on GitHub. A Bloch effective Hamiltonian formalism is also utilized to extract model Hamiltonian parameters from RAS-1SF calculations, allowing more nuanced studies of the Heisenberg J couplings present in many molecules with magnetically coupled sites. Over- all, our work with Fock-space CI provides a way to study magnetic couplings in very large strongly correlated systems at relatively low computational cost. This work was supported by a grant from the U.S. Department of Energy: DE-SC0018326.ETDIn Copyrightelectronic structuretheoretical chemistryspin-flipeffective HamiltoniansDissertation