Density Functional Theory–Broken Symmetry (DFT–BS) Methodology Applied to Electronic and Magnetic Properties of Bioinorganic Prosthetic Groups

Abstract

The goal of this "how to" chapter is to present in a way as simple and practical as possible some of the concepts, key issues, and practices behind the so-called broken symmetry (BS) state which is widely used within the density functional theory (DFT) (for a very nice but thoughtful introduction to DFT (without equations!), read Perdew et al. (J Chem Theory Comput 5:902-908, 2009)) community to compute energetic as well as spectroscopic properties pertaining to (poly-)radicals, bioinorganic clusters (especially those containing transition metal ions), etc. Such properties encompass exchange coupling constants J (molecular magnetism) but also (among other things) g-tensors and hyperfine coupling tensors A (from electron paramagnetic resonance), isomer shifts δ and quadrupolar tensors ΔE Q (from Mössbauer), etc.Hopefully, this chapter will appeal to those DFT practitioners who would like to understand the basics behind the BS state and help them "demystify" some of the issues involved with them. More technical issues will only be alluded to, and appropriate references will be given for those interested to go beyond this mere introduction. This chapter is however not a review of the field. Consequently, it will be primarily based on my own experience. The goal here (in the spirit of a "how to" chapter) is to accompany the readers' thoughts in a progressive way along increasingly complex issues rather than encumbering the same thoughts with too complicate mathematical details (the few derivations which are given will therefore be explicit). Moreover, I will emphasize in this chapter the interplay between the computation of BS states on the one hand, and the derivation of phenomenological models on the other hand, whose parameters can be supplied from appropriate BS states. Finally, this chapter is dedicated to Louis Noodleman (Scripps Research Institute, CA, USA), pioneer (Noodleman, J Chem Phys 74:5737-5743, 1981; Noodleman, Chem Phys 109:131-143, 1986) and leading practitioner (for those interested, I invite them to look for his papers online (via Web of Knowledge for example) as they are simply too numerous to be cited here) of the BS methodology described below in the rich field of (bio)inorganic (transition metal) complexes and prosthetic groups and also a mentor (since my 2-year postdoctoral fellowship with him, back in 1992-1993) and a friend.