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Title

Understanding Electronic Structure and Bonding in Uranium Complexes by Using Computational Methods

Document Type

Oral/Panel

Publication Date

5-2020

Disciplines

Chemistry

Abstract

The electronic structure of actinide-containing complexes is often complex due to the near degeneracies present in the valence orbitals and the ability of both the 5f and 6d orbitals to engage in bonding. Herein we explore the electronic structure of uranium-arene complexes. Previous research has shown that the f orbitals on uranium and πœ‹ electrons from the arene can engage in different types of bonding ranging from strong, highly covalent 𝛿 bonds to polarized donor-acceptor interactions between occupied orbitals on the ligand and empty orbitals on the metal. By using a combination of density functional theory (DFT) and complete active space second order perturbation theory (CASPT2), we can study large complexes while ensuring that the electronic structure is properly described at the DFT level. Specifically, we are studying the[U(anth)2(hmpa)2] complex, 1, (where anth=anthracene and hmpa=hydroxymethylphosphoramide). In addition to the electronic structure, we will explore the nature of bonding in the complex and which orbitals are contributed to forming the bond. Future work will extend this study to 1) larger uranium-arene complexes containing more than one uranium center and 2) packing effects including the role of counterions on the geometry and electronic structure.

First Advisor

Bess Vlaisavljevich

Second Advisor

Skye Fortier

Research Area

Chemistry

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