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TOWARDS SIMULATING ATOMISTIC NONADIABATIC DYNAMICS WITH RING POLYMERS

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Abstract

Many interesting chemical processes feature nonadiabatic dynamics, where the motion of the nuclei are governed by multiple electronic states. Accurate study of these processes requires the use of methods that can include nonadiabatic effects in dynamics simulations. These methods need to be efficient to be considered for use in large scale atomistic simulations, and ideally can incorporate nuclear quantum effects as well. Here we present work aimed to utilize ring polymer (RP)-based methods for future use in atomistic nonadiabatic dynamics.First we demonstrate our development of software for simulating an explicit, quantized electron interacting with a system of classical atoms. This software is used for atomistic RP molecular dynamics (MD) simulations of the cobalt bipyri- dine self-exchange reaction to understand the effect the movement of the charge has on the solvent and ligands of the transition metal complexes (TMCs). By using these simulations along with electronic structure methods, we are able to obtain a rate constant in agreement with experimental results and analyze the motions of the atoms and electron during the reaction. To introduce nonadiabatic effects into RPMD, we make use of the mean field (MF)-RPMD method. We present a new MF-RPMD rate formalism with a novel dividing surface and reaction coordinate and use it to calculate accurate nonadi- abatic and adiabatic rate constants for model condensed phase electron transfer reactions. We test the applicability of MF-RPMD to new chemical processes byusing the method to study polariton chemistry, in particular the control of photoi- somerization caused by the existence of the polariton hybrid states. MF-RPMD offers a very efficient method for performing nonadiabatic dynam- ics, along with including nuclear quantum effects, making it very attractive for use in large scale systems. Implementation of the method in our atomistic RPMD software is the natural progression of this work to achieve atomistic nonadiabatic dynamics.

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97 pages

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2023-08

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Ananth, Nandini

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Lancaster, Kyle
Ezra, Gregory

Degree Discipline

Chemistry and Chemical Biology

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Ph. D., Chemistry and Chemical Biology

Degree Level

Doctor of Philosophy

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Government Document

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Attribution 4.0 International

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dissertation or thesis

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