Electronic Properties of Iron Sites and Their Active Forms in Porphyrin-Type Architectures

  • Mariusz RadońEmail author
  • Ewa Broclawik
Part of the Springer Series on Bio- and Neurosystems book series (SSBN, volume 8)


This chapter is focused on recent advances in quantum chemical modeling of active sites in heme proteins and iron porphyrin complexes. After introducing the computational methods (density functional theory and correlated ab initio ones) several case studies are reviewed to show how these methods unravel the electronic structure of heme and heme-related systems; in particular, how they deal with description of: (a) spin state energetics in ferrous and ferric complexes; (b) binding properties of CO, NO, and \({\text {O}}_{2}\) ligands to heme; (c) electronic structure of P450 Cpd I and alike systems. Making conclusive calculations for the heme species requires a balanced treatment of electron correlation, which is a great challenge for the present computational methods. Further challenge is situated in a correct translation of the computational results into chemical terms. Achievements of modern ab initio methods on the two fronts are highlighted and discussed in relation to DFT calculations.



This research project was supported by grant no UMO-2011/01/B/ST4/02620 from the National Science Centre (Poland) and by grant no IP2011 044471 from the Ministry of Science and Higher Education (Poland). This scholarly work was made thanks to POWIEW project, which is co-funded by the European Regional Development Fund (ERDF) as a part of the Innovative Economy program. This publication was made possible through the financial support from the Foundation for Polish Science (START scholarship provided for M.R.). We also acknowledge computational grants from Academic Computer Center CYFRONET AGH in Kraków, WCSS in Wroclaw (grant no. 181), and CI TASK in Gdańsk.


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Authors and Affiliations

  1. 1.Academic Computer Center CYFRONET AGHKrakówPoland
  2. 2.Faculty of ChemistryJagiellonian University in KrakowKrakówPoland
  3. 3.Jerzy Haber Institute of CatalysisPolish Academy of SciencesKrakówPoland

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