Theoretical Comparison of the Excited Electronic States of the Uranyl and Uranate Ions Using Relativistic Computational Methods
Master's thesis Aug 2002-Mar 2003
AIR FORCE INST OF TECH WRIGHT-PATTERSON AFB OH SCHOOL OF ENGINEERING AND MANAGEMENT
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This thesis examines the ground and excited electronic states of the uranyl UO2 and uranate UO4-2 ions using Hartree-Fock self-consistent field HF SCF, multi-configuration self-consistent field MCSCF and multi-reference single and double excitation configuration interaction MR- CISD methods. The MR-CISD SD calculation included spin-orbit operators. Molecular geometries were obtained from self-consistent field SCF second-order perturbation theory MP2, and density functional theory DFT geometry optimizations using the NWChem 4.01 massively parallel ab initio software package. COLUMBUS version 5.8 was used to perform in-depth analysis on the HF SCF MCSCF and MR-CISD potential energy surfaces. Excited state calculations for the uranyl ion were performed using both a large- and small-core relativistic effective core potential RECP in order to calibrate the method. This calibration included comparison to previous theoretical and experimental work on the uranyl ion. Uranate excited states were performed using the small-core RECP as well as the methodology developed using the uranyl ion.
- Organic Chemistry
- Quantum Theory and Relativity