Dissertation
ACCURATE AB INITIO THERMOCHEMISTRY AND SPECTROSCOPY OF MOLECULES CONTAINING TRANSITION METALS AND HEAVY ELEMENTS.
Doctor of Philosophy (PhD), Washington State University
01/2015
Handle:
https://hdl.handle.net/2376/117226
Abstract
Composite thermochemistry schemes are routinely applied to systems containing a few light elements and are capable of chemical accuracy (±1 kcal/mol) or better. Their applications in heavier systems have been significantly limited due to the necessity of considering both special relativity and the effects of near degenerate orbitals. This work explores applying the Feller Peterson Dixon (FPD) methodology, and how each of its aspects can be addressed, in molecules containing heavy elements and transition metals for both thermochemical and spectroscopic applications. The work is divided into seven chapters and five appendices.
The first chapter offers a brief introduction followed by a review of the computational methods used in these works and a summary of the current results and conclusions.
Chapter two studies the dependence of the atomization energies of 3d transition metal-containing molecules on both basis set convergence and higher order correlation.
Chapter three presents the development of new all electron Gaussian basis sets for the 5p and 6p elements based on a scalar relativistic Hamiltonian.
Chapter four applies the FPD scheme to U6+ containing molecules for the first time with excellent agreement (1 kcal/mol) found between both all-electron and analogous pseudopotential-based approaches to relativity.
Chapter five offers a theoretical prediction of the spectroscopy of UCl and UCl+ based on a detailed examination of UF, UF+, and U+. The latter are compared to available experimental spectroscopic data.
Chapter six determines the first six ionization potentials of the uranium atom using a composite multireference configuration interaction based approach.
Chapter seven presents a systematic investigation of the UFO molecule starting with closed shell UFO3+ and finishing with UFO–.
The first three appendices (A-C) give the additional supporting information from Chapters two, five, and six respectively.
The fourth (D) and fifth (E) appendices offer hands-on guides to technical details necessary for the work of Chapters five and six, respectively. The fourth shows how to assign Ω states from the state interacting method of molpro . The fifth shows how to generate inputs for calculating the Davidson correction in the dirac program. Both include the programs used to automate these procedures.
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Details
- Title
- ACCURATE AB INITIO THERMOCHEMISTRY AND SPECTROSCOPY OF MOLECULES CONTAINING TRANSITION METALS AND HEAVY ELEMENTS.
- Creators
- David Hamilton Bross
- Contributors
- Kirk A Peterson (Advisor)Kirk A Peterson (Committee Member)Aurora E Clark (Committee Member)Kerry W Hipps (Committee Member)James A Brozik (Committee Member)
- Awarding Institution
- Washington State University
- Academic Unit
- Chemistry, Department of
- Theses and Dissertations
- Doctor of Philosophy (PhD), Washington State University
- Number of pages
- 370
- Identifiers
- 99900581526301842
- Language
- English
- Resource Type
- Dissertation