Simulation of defects in molecular materials using ab initio methods
| dc.contributor.advisor | Hendon, Christopher | |
| dc.contributor.author | Gormley, Eoghan | |
| dc.date.accessioned | 2025-02-24T19:58:33Z | |
| dc.date.issued | 2025-02-24 | |
| dc.description.abstract | Molecular materials such as metal-organic frameworks (MOFs) are emerging as an interesting class of materials for their wide range of applications as well as their customizability and tunability. Like other materials, the properties of molecular materials can be modified through the use of defects - however, the nature of these defects in these systems can be much more complex than in conventional materials. Because of this, modifying conventional computational methods is essential for understanding defects in these systems. This research addresses the limitations of traditional approaches by refining techniques for calculating chemical potentials and employing higher levels of theory, such as many- body perturbation theory (MBPT), to model the unique electronic structures of MOFs. These modifications attempt to account for the intricate chemical environments, large unit cells, and significant structural dynamics inherent to molecular materials. We propose that chemical potentials for defects should be calculated based on the reactions that form the defects, thereby incorporating the thermodynamics of covalent bond formation and cleavage, as opposed to referencing them to elemental phases and treating all atoms of a given species as thermodynamically equivalent. We also attempt to use MBPT to more accurately predict the electronic properties of these materials (thereby overcoming the underestimations of fundamental band gaps typical of simpler ab initio methods)which is essential to predict the stability of defects that these materials can host. Finally, a case study on Yttrium-based MOFs with HHTP linkers demonstrated the potential impact of defects and guest ions on conductivity, showcasing the practical implications of accurate defect modeling. Theoretical findings enhance the predictive power of computational methods for MOFs, informing material design and optimization for applications in catalysis, gas storage, and electronic devices. This dissertation includes previously published coauthored material. | en_US |
| dc.description.embargo | 2025-10-30 | |
| dc.identifier.uri | https://hdl.handle.net/1794/30471 | |
| dc.language.iso | en_US | |
| dc.publisher | University of Oregon | |
| dc.rights | All Rights Reserved. | |
| dc.subject | Catalysis | en_US |
| dc.subject | Defects | en_US |
| dc.subject | Electronic Structure | en_US |
| dc.subject | Materials | en_US |
| dc.subject | Simulation | en_US |
| dc.title | Simulation of defects in molecular materials using ab initio methods | |
| dc.type | Electronic Thesis or Dissertation | |
| thesis.degree.discipline | Department of Chemistry and Biochemistry | |
| thesis.degree.grantor | University of Oregon | |
| thesis.degree.level | doctoral | |
| thesis.degree.name | Ph.D. |