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Exploring the high sensitivity of DFT thermochemistry for protonation states of a ferredoxin model complex [ C H 3 S 4 Fe 2 III S 2 H ] −

Vysotskiy, Victor P. LU and Ryde, Ulf LU orcid (2025) In Journal of Chemical Physics 162(16).
Abstract

Density functional theory (DFT) thermochemistry of 3d transition-metal complexes is well-known to be sensitive to the amount of exact Hartree-Fock exchange incorporated into the exchange-correlation functional. For example, relative energies of different protonation states of iron-sulfur complexes may vary by hundreds of kJ/mol among different DFT methods. In the present study, we examine the relative energies of four protonation isomers of the [ C H 3 S 4 Fe 2 III S 2 H ] − [2Fe-2S] ferredoxin model. Compared to many-body ab initio phaseless auxiliary-field quantum Monte Carlo with multi-Slater determinant trial wavefunctions and fully connected singles and doubles coupled-cluster with perturbative triples methods, the... (More)

Density functional theory (DFT) thermochemistry of 3d transition-metal complexes is well-known to be sensitive to the amount of exact Hartree-Fock exchange incorporated into the exchange-correlation functional. For example, relative energies of different protonation states of iron-sulfur complexes may vary by hundreds of kJ/mol among different DFT methods. In the present study, we examine the relative energies of four protonation isomers of the [ C H 3 S 4 Fe 2 III S 2 H ] − [2Fe-2S] ferredoxin model. Compared to many-body ab initio phaseless auxiliary-field quantum Monte Carlo with multi-Slater determinant trial wavefunctions and fully connected singles and doubles coupled-cluster with perturbative triples methods, the r2SCAN12-D4, B3LYP-D4, and B97-1-D3(OP) approaches perform the best. We also demonstrate that density-corrected DFT on top of KS-CCSD electronic densities provides reliable results with the r2SCAN functional. Moreover, the direct random phase approximation on top of the TPSSh, O3LYP, and r2SCAN12 hybrid functionals performs well.

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type
Contribution to journal
publication status
published
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in
Journal of Chemical Physics
volume
162
issue
16
article number
165101
publisher
American Institute of Physics (AIP)
external identifiers
  • pmid:40260822
  • scopus:105003321426
ISSN
0021-9606
DOI
10.1063/5.0261086
language
English
LU publication?
yes
additional info
Publisher Copyright: © 2025 Author(s).
id
c7e28df6-f86f-4369-b8d0-cd4dad112bbf
date added to LUP
2025-08-06 10:46:06
date last changed
2025-08-07 02:55:45
@article{c7e28df6-f86f-4369-b8d0-cd4dad112bbf,
  abstract     = {{<p>Density functional theory (DFT) thermochemistry of 3d transition-metal complexes is well-known to be sensitive to the amount of exact Hartree-Fock exchange incorporated into the exchange-correlation functional. For example, relative energies of different protonation states of iron-sulfur complexes may vary by hundreds of kJ/mol among different DFT methods. In the present study, we examine the relative energies of four protonation isomers of the [ C H 3 S 4 Fe 2 III S 2 H ] − [2Fe-2S] ferredoxin model. Compared to many-body ab initio phaseless auxiliary-field quantum Monte Carlo with multi-Slater determinant trial wavefunctions and fully connected singles and doubles coupled-cluster with perturbative triples methods, the r<sup>2</sup>SCAN12-D4, B3LYP-D4, and B97-1-D3(OP) approaches perform the best. We also demonstrate that density-corrected DFT on top of KS-CCSD electronic densities provides reliable results with the r<sup>2</sup>SCAN functional. Moreover, the direct random phase approximation on top of the TPSSh, O3LYP, and r<sup>2</sup>SCAN12 hybrid functionals performs well.</p>}},
  author       = {{Vysotskiy, Victor P. and Ryde, Ulf}},
  issn         = {{0021-9606}},
  language     = {{eng}},
  month        = {{04}},
  number       = {{16}},
  publisher    = {{American Institute of Physics (AIP)}},
  series       = {{Journal of Chemical Physics}},
  title        = {{Exploring the high sensitivity of DFT thermochemistry for protonation states of a ferredoxin model complex [ C H 3 S 4 Fe 2 III S 2 H ] −}},
  url          = {{http://dx.doi.org/10.1063/5.0261086}},
  doi          = {{10.1063/5.0261086}},
  volume       = {{162}},
  year         = {{2025}},
}