Subject Area
Chemistry, Physics
Abstract
The bottommost part of the periodic table has a unique chemistry, where the high velocities of the inner-shell electrons prevent their description by the usual Schrödinger equation. The resulting so-called relativistic effects have numerous chemical implications, on both macro and microscale, ranging from physical properties to reactivity. However, experimental probes on these intriguing atoms are limited by their natural availability and, more importantly, the danger associated with their radioactivity. Quantum chemical calculations, on the other hand, face the challenge of far more complex algebra, which demands substantial computational resources. Relativistic Hamiltonians, which act over all electrons in the system, are currently among the most accurate methods used to describe the electronic structure of heavy atoms. Over the years, the Normalized Elimination of the Small Component (NESC) Hamiltonian, originally proposed by Dyall, has been extensively improved by the CATCO group; the latest version, NESC with atomic unitary transformation (NESCau), allows for accurate calculations on large systems at a reasonable cost.
In this dissertation, we applied the NESC and NESCau Hamiltonians, paired with the well-established theories of local vibrational mode analysis (LMA) and quantum theory of atoms in molecules (QTAIM), to describe chemical bonding in heavy atoms. Our results showcase intriguing aspects of the chemistry of uranium and lanthanides, including their geometry, bonding mechanisms, and chemical affinities.
Degree Date
Summer 2024
Document Type
Dissertation
Degree Name
Ph.D.
Department
Chemistry
Advisor
Elfi Kraka
Number of Pages
145
Format
Creative Commons License
This work is licensed under a Creative Commons Attribution-Noncommercial 4.0 License
Recommended Citation
Teixeira Costa Peluzo, Barbara Maria, "The Chemistry of Heavy Elements: Probing Relativistic Chemical Bonding" (2024). Chemistry Theses and Dissertations. 49.
https://scholar.smu.edu/hum_sci_chemistry_etds/49
Included in
Computational Chemistry Commons, Inorganic Chemistry Commons, Materials Chemistry Commons, Quantum Physics Commons
