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Understanding semi-core 4f-covalency in novel lanthanide compounds Henry Harrell Wilson
- Format:
- Book
- Thesis/Dissertation
- Author/Creator:
- Wilson, Henry Harrell, author.
- Language:
- English
- Subjects (All):
- Chemistry.
- Inorganic chemistry.
- Analytical chemistry.
- 0485.
- 0488.
- 0486.
- Local Subjects:
- Chemistry.
- Inorganic chemistry.
- Analytical chemistry.
- 0485.
- 0488.
- 0486.
- Genre:
- Academic theses
- Physical Description:
- 1 online resource (294 pages)
- Contained In:
- Dissertations Abstracts International 87-12B
- Place of Publication:
- Ann Arbor : ProQuest Dissertations and Theses, 2025
- Language Note:
- English
- Summary:
- The lanthanides were long considered limited to ionic bonding due to the "core-like" nature of their valence 4f-orbitals; however, there is growing evidence to support semi-core 4f covalency, which can give rise to unusual electronic structures including multiconfigurational ground states. This dissertation focuses on the synthesis of lanthanide and actinide complexes with novel bonding modes, and the characterization of their electronic structures through a synergy of spectroscopic and computational techniques. Chapter 2 investigates covalency differences in isostructural cerium and thorium parent amide complexes, establishing that subtle electronic structure changes can produce large differences in observable properties. Chapter 3 details the isolation and characterization of a unique Ce(IV) bridging nitride complex, where calculations reveal significant metal-ligand covalency mediated by 4f/5d hybridization. Chapter 4 reports a rare homoleptic organocerium(IV) compound with a multiconfigurational ground state. The leading open-shell singlet Ce(III) 4f1 configuration designates it an example of a self-contained Kondo system, mimicking the strong electron correlations of solid-state analogs. Understanding the criteria governing this behavior holds promise for the rational design of new quantum materials. Collectively, these findings deepen our understanding of 4f-orbital semi-core covalency and its role in lanthanide bonding and electronic structure
- Notes:
- Source: Dissertations Abstracts International, Volume: 87-12, Section: B.
- Advisors: Schelter, Eric J.; Mallouk, Thomas E. Committee members: Walsh, Patrick J.; Mindiola, Daniel J.
- Ph.D. University of Pennsylvania 2025
- Vendor supplied data
- Local Notes:
- School code: 0175
- ISBN:
- 9798247982173
- Access Restriction:
- Restricted for use by site license
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