RESEARCH ARTICLE
Assessing Electronic-Structure Methods for Redox Potentials of an Iron-Sulfur Cluster
Lukas Hehn,
Peter Deglmann,
Michael Kühn,
Lukas Hehn
BASF SE, Next Generation Computing, Ludwigshafen, Germany
Search for more papers by this authorPeter Deglmann
BASF SE, Quantum Chemistry, Ludwigshafen, Germany
Search for more papers by this authorCorresponding Author
Michael Kühn
BASF SE, Next Generation Computing, Ludwigshafen, Germany
Correspondence: Michael Kühn ([email protected])
Search for more papers by this authorLukas Hehn,
Peter Deglmann,
Michael Kühn,
Lukas Hehn
BASF SE, Next Generation Computing, Ludwigshafen, Germany
Search for more papers by this authorPeter Deglmann
BASF SE, Quantum Chemistry, Ludwigshafen, Germany
Search for more papers by this authorCorresponding Author
Michael Kühn
BASF SE, Next Generation Computing, Ludwigshafen, Germany
Correspondence: Michael Kühn ([email protected])
Search for more papers by this authorFirst published: 13 June 2025
Funding: This work was supported by the German Federal Ministry of Education and Research (BMBF) within the funding program “Quantum technologies—From basic research to market” in the joint project MANIQU (Grant No. 13N15575).
ABSTRACT
Iron-sulfur (FeS) clusters play a crucial role in biological redox processes. In this study, we evaluate the accuracy of various electronic-structure methods for calculating the redox potentials of the synthetic [Fe4S4(SC(CH3)3)4] cluster by comparing them to experimental data. Our assessment includes a range of density functionals within broken-symmetry density functional theory (BS-DFT), the most commonly used approach for this purpose, though it has not yet been systematically compared to other methods. We also explore correlated methods such as the random phase approximation (RPA) and auxiliary-field quantum Monte Carlo (AFQMC), which are rarely applied to FeS clusters, as well as complete active space (CAS) methods combined with density matrix renormalization group (DMRG) theory and various active space constructions. Among these, BS-DFT with the hybrid functionals B3LYP, PBE0, and TPSSh showed the highest accuracy, together with RPA in combination with the approximate exchange kernel (AXK). While AFQMC demonstrated some promise, DMRG-CAS methods were significantly less accurate, likely due to inconsistencies between the active spaces within a redox pair.
Conflicts of Interest
The authors declare no conflicts of interest.
Open Research
Data Availability Statement
The data that supports the findings of this study are available in the Supporting Information of this article.
Supporting Information
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| qua70068-sup-0001-supinfo.pdfPDF document, 2.3 MB | Data S1. Supporting Information. |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
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