The Ligand-Field Paradigm-Insight into Electronic Properties of 
Transition-metal Complexes Based on Calculations of Electronic Structure

Atanasov, Mihail; Comba, Peter; Daul, Claude A.; Neese, Frank

doi:10.1007/978-1-4020-5941-4_19

Item

ITEM ACTIONSEXPORT

Add to Basket

Local TagsRelease HistoryDetailsSummary

Released

Book Chapter

The Ligand-Field Paradigm-Insight into Electronic Properties of Transition-metal Complexes Based on Calculations of Electronic Structure

MPS-Authors

There are no MPG-Authors in the publication available

External Resource

No external resources are shared

Fulltext (restricted access)

There are currently no full texts shared for your IP range.

Fulltext (public)

There are no public fulltexts stored in PuRe

Supplementary Material (public)

There is no public supplementary material available

Citation

Atanasov, M., Comba, P., Daul, C. A., & Neese, F. (2008). The Ligand-Field Paradigm-Insight into Electronic Properties of Transition-metal Complexes Based on Calculations of Electronic Structure. In J. C. A. Boeyens, & J. F. Ogilvie (Eds.), Models, Mysteries and Magic of Molecules (pp. 411-446). Dordrecht, The Netherlands: Springer.

Cite as: https://hdl.handle.net/21.11116/0000-0008-33B4-3

Abstract

An overview and a critical comparison of contemporary models to describe and to predict electronic multiplet structures and the spectroscopic behavior of transition-metal complexes with open d-shells is given in relation to experimental data including d-d absorption and ESR spectra. A ligand-field density-functional theory (LFDFT) predicts these properties with a success similar to ab initio approaches, such as the spectroscopy oriented configuration-interaction method, and better than time-dependent density-functional theory applied to open shell systems. Using well characterized systems, from classical coordination compounds [FeO₄]^2-, CrX₆^3- (X=F,Cl), CoL₆^z(z=-3, L=CN^-; z=2 and 3, L=H₂O)] to Fe^IV macrocyclic compounds with biochemical and catalytic activity, it is shown that LFDFT is able also to characterize larger systems and subtle effects such as those from surrounding influences and the second coordination sphere.