Probing the performance of DFT in the structural characterization of [ FeFe ] hydrogenase models
Year: 2024
Type: article
Abstract: In this work, a series of DFT and DFT‐D methods is combined with double‐ ζ basis sets to benchmark their performance in predicting the structures of five newly synthesized hexacarbonyl diiron complexes with a bridging ligand featuring a μ ‐S 2 C 3 motif in a ring‐containing unit functionalized with aromatic groups. Such complexes have been considered as [FeFe] hydrogenase catalytic site models with potential for eco‐friendly energetic applications. According to this assessment, r 2 SCAN is identified as the density functional recommended for the reliable description of the molecular and crystal structures of the herein studied models. However, the butterfly ( μ ‐S) 2 Fe 2 core of the models demonstrates a minor deformation of its optimized geometry obtained from both molecular and periodic calculations. The FeFe bond length is slightly underestimated while the FeS bonds tend to be too long. Adding the D3(BJ) correction to r 2 SCAN does not lead to any improvement in the calculated structures.
DOI: 10.1002/jcc.27515
Institutions: University of Łódź, Friedrich Schiller University Jena
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: bronze
OpenAlex ID: W4403491350