Applied Computational Actinide Chemistry

Andr Severe Pereira Gomes, FlorentReal, Bernd Schimmelpfennig, UlfWahlgren,  

Computational Methods in Lanthanide and Actinide Chemistry, First Edition. Edited by Michael Dolg. 2015 John Wiley Sons, Ltd. Published 2015 by John Wiley Sons, Ltd. 

In this chapter we aim to diseuss the requirements, challenges, and pitfalls associated with attempting to theoretically model molecular properties for such systems that can be directly compared to experimental data, such as valence excitation spectra, core-excitation spectra, thermodynamics of chemical reactions, and redox properties. 

1 Relativistic Correlated Methods for Ground and Excited States 

A thorough review of electronic structure methods is outside the scope of this chapter, and we therefore refer the reader to a non-exhaustive list of recent review papers [3-9] for further reading. 

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Gas-phase chemistry studies of atomic and molecular rare-earth and actinide ions have a deep-rooted history of more than three decades. In gas phase, physical and chemical properties of elementary and molecular species can be studied in absence of external perturbations. Due to the relative simplicity of gas-phase systems compared to condensed-phase systems, solutions or solids, it is possible to probe in detail the relationships between electronic structure, reactivity, and energetics. Most of this research involves the use of a variety of mass spectrometry techniques, which allows one exerting precise control over reactants and products. Many new rare earth and actinide molecular and cluster species have been identified that have expanded knowledge of the basic chemistry of these elements and provided clues for understanding condensed-phase processes. Key thermodynamic parameters have been obtained for numerous atomic and molecular ions. Such fundamental physicochemical studies have provided opportunities for the refinement and validation of computational methods as applied to the particularly challenging lanthanide and actinide elements. Among other applications, the roles of... 

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