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dc.contributor.authorKenion-Hanrath, Rachel
dc.identifier.otherbibid: 9905941
dc.description.abstractQuantum effects like tunneling, coherence, and zero point energy often play a significant role in phenomena on the scales of atoms and molecules. However, the exact quantum treatment of a system scales exponentially with dimensionality, making it impractical for characterizing reaction rates and mechanisms in complex systems. An ongoing effort in the field of theoretical chemistry and physics is extending scalable, classical trajectory-based simulation methods capable of capturing quantum effects to describe dynamic processes in many-body systems; in the work presented here we explore two such techniques. First, we detail an explicit electron, path integral (PI)-based simulation protocol for predicting the rate of electron transfer in condensed-phase transition metal complex systems. Using a PI representation of the transferring electron and a classical representation of the transition metal complex and solvent atoms, we compute the outer sphere free energy barrier and dynamical recrossing factor of the electron transfer rate while accounting for quantum tunneling and zero point energy effects. We are able to achieve this employing only a single set of force field parameters to describe the system rather than parameterizing along the reaction coordinate. Following our success in describing a simple model system, we discuss our next steps in extending our protocol to technologically relevant materials systems. The latter half focuses on the Mixed Quantum-Classical Initial Value Representation (MQC-IVR) of real-time correlation functions, a semiclassical method which has demonstrated its ability to ``tune'' between quantum- and classical-limit correlation functions while maintaining dynamic consistency. Specifically, this is achieved through a parameter that determines the quantumness of individual degrees of freedom. Here, we derive a semiclassical correction term for the MQC-IVR to systematically characterize the error introduced by different choices of simulation parameters, and demonstrate the ability of this approach to optimize MQC-IVR simulations.
dc.subjectelectron transfer
dc.subjectlarge-scale simulations
dc.subjectmixed quantum-classical initial value representation
dc.subjectpath integral methods
dc.subjectquantum effects
dc.subjectsemiclassical methods
dc.subjectTheoretical physics
dc.typedissertation or thesis Engineering University of Philosophy D., Chemical Engineering
dc.contributor.chairAnanth, Nandini
dc.contributor.chairEscobedo, Fernando
dc.contributor.committeeMemberLoring, Roger F
dc.contributor.committeeMemberDuncan, Thomas Michael

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