Orbitals for Analyzing Bonding and Magnetism of Heavy-Metal Complexes

Abstract

Electron orbitals are ubiquitous in chemistry for the description of bonding and molecular properties. This article outlines a theoretical framework for the generation and application of orbitals for the analysis of the electronic structure, chemical bonding, and magnetic properties of metal complexes from relativistic quantum chemical wavefunction calculations. Examples from the author’s research of f-element complexes are used to illustrate these concepts, with emphasis on open-shell systems.

GRAPHICAL ABSTRACT

Acknowledgments

The author thanks Dr. Benjamin Pritchard and Dr. Frédéric Gendron for their contributions to the studies of f-element complexes and the development of the computational tools discussed herein, Dr. Hélène Bolvin for an on-going productive and scientifically stimulating collaboration, Dr. Frédéric Gendron for preparing several of the figures, the Center for Computational Research (CCR) at the University at Buffalo for providing computational resources, and Prof. Timothy Cook for valuable comments on the manuscript.

Additional information

Funding

The author acknowledges financial support for his theoretical studies of the magnetic properties of f-element complexes from the U.S. Department of Energy, Office of Basic Energy Sciences, Heavy Element Chemistry program, under grant DE-SC0001136 (formerly DE-FG02-09ER16066).