The reparametization of semiempirical Hamiltonians is an emerging method used in direct dynamics studies. The use of semiempirical Hamiltonians in direct dynamics studies diminishes the computational cost of trajectory calculations and negates the need for an analytical potential energy surface when performing reaction dynamics studies. The reparametization of semiempirical Hamiltonians increases the agreement with experiment and high level ab initio theory. We have chosen to create one set of new parameters that apply to two related reactions, F + CH₄ → HF + CH₃ and F + C₂H₆ → HF + C₂H₅. We have performed an electronic structure study for these reactions. The ab initio data obtained from the electronic structure study is then used as the reference for a reparametization of the PM3 Hamiltonian. The reparametization has improved the ab initio and PM3 reaction energy and potential energy surface scan agreement. This new set of parameters for PM3 (SRP-PM3) is used to perform a direct quasiclassical trajectory study of the reactions. The vibrational and rotational HF distributions calculated using SRP-PM3 are compared with experiments. We have observed an improvement in the agreement with experimental vibrational distributions but have seen no change in the rotational distributions. / Master of Science

Organometallic reactions are a fundamental class of chemical transformations. The mechanisms of organometallic reactions are routinely modeled by calculating intermediates and transition-state structures on a potential energy surface with density functional theory (DFT). The translation of these calculated structures to a reaction mechanism is typically done under the umbrella of statistical transition state theory. This dissertation reports the use of DFT calculations and quasiclassical direct dynamics trajectories to explore the possibility of nonstatistical dynamic effects in organometallic reactions. Chapter 1 provides a brief review of potential energy surfaces, transition state theory, dynamics trajectories, and a review of previous dynamics studies of organometallic reactions. Chapter 2 reports dynamics trajectories of an organometallic β–hydride transfer reaction with Rh, Ir, and Co metal centers. This chapter was previously published as Dalton Trans. 2020, 49, 7747-7757. Chapters 3 reports the potential energy surface and structures for benzene reductive elimination for dimethyl silyl-bridged W and Mo metallocene complexes. Chapter 4 reports gas-phase and explicit solvent dynamics trajectories for this benzene reductive elimination reaction.