Quantum Chemical Insights into the Periodicity and Electronic Structures of Actinide Complexes

Abstract

This PhD thesis presents a quantum chemical study of actinide complexes newlinewith organic ligands using Density Functional Theory (DFT). The physical and electronic newlineproperties and energetics of these complexes were investigated to determine trends in newlineactinide behaviour across the 5f series. newlineChapter 1 is an introduction to actinide chemistry, the role of organic newlinemolecules as ligands and their modifications for actinide coordination, and the newlinecomputational analyses for the study of the electronic and energetic parameters of actinide newlinecomplexes. Chapter 2 is a computational study of modelled high-valent actinyl (An = U newlineto Np) - tetraquinoline (TEQ) complex based on experimental work reported on transition newlinemetal complexes. The quantum chemical calculations of their geometric, electronic and newlineenergy parameters suggest the potential of TEQ for actinide complexation and the newlineproperties of actinides. Chapter 3 investigates the stabilization of high-valent actinyls (An newline= U to Am) using pyrrophen ligands which offer a diverse donor environment (i.e., N and newlineO atoms). Chapter 4 focuses on the competitive complexation of americium (Am3+) and newlinecurium (Cm3+) in their trichloride form with core-modified dipyriamethyrin ligands, newlineaddressing the challenge of minor actinide separation newline