Importance of Electron Correlation on the Geometry and Electronic Structure of [2Fe-2S] Systems: A Benchmark Study of the [Fe2S2(SCH3)4]2-,3-,4-, [Fe2S2(SCys)4]2-, [Fe2S2(S-p-tol)4]2-, and [Fe2S2(S-o-xyl)4]2- Complexes

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F24%3A00602170" target="_blank" >RIV/61388955:_____/24:00602170 - isvavai.cz</a>

Result on the web

<a href="https://pubs.acs.org/doi/10.1021/acs.jctc.4c00781" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jctc.4c00781</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jctc.4c00781" target="_blank" >10.1021/acs.jctc.4c00781</a>

Result language

angličtina

Original language name

Importance of Electron Correlation on the Geometry and Electronic Structure of [2Fe-2S] Systems: A Benchmark Study of the [Fe2S2(SCH3)4]2-,3-,4-, [Fe2S2(SCys)4]2-, [Fe2S2(S-p-tol)4]2-, and [Fe2S2(S-o-xyl)4]2- Complexes

Original language description

Iron-sulfur clusters are crucial for biological electron transport and catalysis. Obtaining accurate geometries, energetics, manifolds of their excited electronic states, and reduction energies is important to understand their role in these processes. Using a [2Fe-2S] model complex with FeII and FeIII oxidation states, which leads to different charges, i.e., [Fe2S2(SMe)4]2-,3-,4-, we benchmarked a variety of computational methodologies ranging from density functional theory (DFT) to post-Hartree-Fock methods, including complete active space self-consistent field (CASSCF), multireference configuration interaction, the second-order N-electron valence state perturbation theory (NEVPT2), and the linearized integrand approximation of adiabatic connection (AC0) approaches. Additionally, we studied three experimentally well-characterized complexes, [Fe2S2(SCys)4]2-, [Fe2S2(S-o-tol)4]2-, and [Fe2S2(S-o-xyl)4]2-, via DFT methods. We conclude that the dynamic electron correlation is important for accurately predicting the geometry of these complexes. Broken symmetry (BS) DFT correctly predicts experimental geometries of low-spin multiplicity, while CASSCF does not. However, BS-DFT significantly overestimates the difference between the low- and high-spin electronic states for a given oxidation state. At the same time, CASSCF underestimates it but provides relative energies closer to the reference NEVPT2 results. Finally, AC0 provides energetics of NEVPT2 quality with the additional advantage of being able to use large CASSCF sizes. NEVPT2 gives the best estimates of the FeIII/FeIII> FeII/FeIII (4.27 eV) and FeII/FIII> FeII/FII (7.72 eV) reduction energies. The results provide insight into the electronic structure of these complexes and assist in the understanding of their physical properties.

Czech name

—

Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/EH22_008%2F0004558" target="_blank" >EH22_008/0004558: Advanced MUltiscaLe materials for key Enabling Technologies</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2024

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Chemical Theory and Computation

ISSN

1549-9618

e-ISSN

1549-9626

Volume of the periodical

20

Issue of the periodical within the volume

23

Country of publishing house

US - UNITED STATES

Number of pages

18

Pages from-to

10406-10423

UT code for WoS article

001358996100001

EID of the result in the Scopus database

2-s2.0-85209720909