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Simulation of nonadiabatic charge transfer during molecular scattering at metal surfaces
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Corken, Daniel (2023) Simulation of nonadiabatic charge transfer during molecular scattering at metal surfaces. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b3980887~S15
Abstract
The development of the next generation of heterogeneous catalysts requires a deep understanding of the fundamental processes that occur when molecules interact with metal surfaces. A key challenge to this goal is that nonadiabatic processes represent a key energy dissipation pathway when molecules interact with metal surfaces.
Such processes lay outside the Born-Oppenheimer potential energy surface (PES) picture that is ubiquitous throughout chemistry and upon which electronic structure methods in computational chemistry rely. Modeling such systems is challenging because they combine large inhomogeneous models, in-plane periodicity with a need to combine electronic excitations with vibrational effects.
The dynamics algorithm independent electron surface hopping (IESH), which attempts to account for nonadiabatic effects when molecules interact with metal surfaces, has shown promise in reproducing experimental observations. IESH simulations require two diabatic PESs, of neutral and anionic charge transfer states. This thesis aims to create accurate diabatic PESs using the linear expansion delta self-consistent field (le-ΔSCF) excited state method. The two forms of le-ΔSCF, density based (ρle-ΔSCF) and wavefunction based (Ψle-ΔSCF) are assessed for the systems of NO-Au(111) and CO-Au(111). Only ρle-ΔSCF is shown to be a viable methodology for constructing charge constrained diabatic PESs due to SCF convergence issues. A new methodology for defining charge constraints in ρle-ΔSCF, which accounts for charge transfer between molecule and metal in the ground state, is developed and used to construct 2D diabatic PESs as a function of molecule-surface separation and molecule bond length, for CO interacting with Au(111) and Ag(111). IESH dynamics simulations of CO scattering from Au(111) and Ag(111) across a range of initial vibrational states and translational kinetic energies are performed and the results are compared to other methods and to experiment.
Item Type: | Thesis (PhD) | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Charge transfer, Electrons -- Scattering, Metals -- Surfaces | ||||
Official Date: | June 2023 | ||||
Dates: |
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Institution: | University of Warwick | ||||
Theses Department: | Department of Chemistry | ||||
Thesis Type: | PhD | ||||
Publication Status: | Unpublished | ||||
Supervisor(s)/Advisor: | Maurer, Reinhard ; Hine, Nicholas | ||||
Format of File: | |||||
Extent: | xx, 176 pages : illustrations | ||||
Language: | eng |
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