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Simulation of nonadiabatic molecular dynamics at metal surfaces
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Gardner, James (2023) Simulation of nonadiabatic molecular dynamics at metal surfaces. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b3985163
Abstract
This thesis is concerned with the numerical simulation ofmolecules interacting with metal surfaces, important to a wide range of processes in the energy sector including the generation and storage of alternative fuels such as hydrogen and for the production of chemicals using heterogeneous catalysis. A complexity of the molecule-metal interaction is the coupled motion of the nuclei and electrons that precludes a treatment of the problem using classical molecular dynamics techniques. The primary objective of the thesis is to treat this complexity by developing methods that can accurately and efficiently simulate the coupled nuclear-electronic dynamics and incorporate nuclear quantum effects that may arise due to the small mass of the molecule.This is achieved by first developing a software framework for the simulation of nonadiabatic molecular dynamics: NQCDynamics.jl, where a collection of existing methods are implemented and benchmarked. Using NQCDynamics.jl, the independent electron surface hopping (IESH) method is investigated and augmented, with its validity examined by benchmarking against quantum dynamics simulations. A comprehensive comparison is then obtained between the predominant methods for dynamics at surfaces including the broadened classical master equation, Ehrenfest dynamics, molecular dynamics with electronic friction, and IESH. During the comparison, a new model is introduced that bridges the gap between simple, one-dimensional models and full-dimensional, atomistic simulations. Finally, nuclear quantum effects are included in each of the existing methods by incorporating the imaginary-time path integral formalism that approximately includes nuclear quantum effects using a ring polymer representation for the nuclei.This work marks the first time that a wide range of methods for simulating dynamics at surfaces have been made available in the same software package and have been benchmarked together on the same systems. Furthermore, the use of the ring polymer formalism for the inclusion of nuclear quantum effects promises to be a viable strategy for the extension of these mixed quantum-classical methods.
Item Type: | Thesis (PhD) | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Metals -- Surfaces, Surface chemistry, Molecular dynamics, Energy storage | ||||
Official Date: | August 2023 | ||||
Dates: |
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Institution: | University of Warwick | ||||
Theses Department: | Department of Chemistry | ||||
Thesis Type: | PhD | ||||
Publication Status: | Unpublished | ||||
Supervisor(s)/Advisor: | Habershon, Scott ; Maurer, Reinhard | ||||
Sponsors: | Leverhulme Trust | ||||
Format of File: | |||||
Extent: | xxiii, 161 pages : illustrations | ||||
Language: | eng |
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