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Assessment of DFT functionals for a minimal nitrogenase [Fe(SH)4H]− model employing state-of-the-art ab initio methods

Vysotskiy, Victor P. LU ; Torbjörnsson, Magne LU ; Jiang, Hao LU orcid ; Larsson, Dennis LU ; Cao, Lili LU ; Ryde, Ulf LU orcid ; Zhai, Huanchen ; Lee, Seunghoon and Chan, Garnet Kin-Lic (2023) In The Journal of chemical physics 159(4).
Abstract
We have designed a [Fe(SH)4H]− model with the fifth proton binding either to Fe or S. We show that the energy difference between these two isomers (∆E) is hard to estimate with quantum-mechanical (QM) methods. For example, different density functional theory (DFT) methods give ∆E estimates that vary by almost 140 kJ/mol, mainly depending on the amount of exact Hartree–Fock included (0%–54%). The model is so small that it can be treated by many high-level QM methods, including coupled-cluster (CC) and multiconfigurational perturbation theory approaches. With extrapolated CC series (up to fully connected coupled-cluster calculations with singles, doubles, and triples) and semistochastic heat-bath configuration interaction methods, we obtain... (More)
We have designed a [Fe(SH)4H]− model with the fifth proton binding either to Fe or S. We show that the energy difference between these two isomers (∆E) is hard to estimate with quantum-mechanical (QM) methods. For example, different density functional theory (DFT) methods give ∆E estimates that vary by almost 140 kJ/mol, mainly depending on the amount of exact Hartree–Fock included (0%–54%). The model is so small that it can be treated by many high-level QM methods, including coupled-cluster (CC) and multiconfigurational perturbation theory approaches. With extrapolated CC series (up to fully connected coupled-cluster calculations with singles, doubles, and triples) and semistochastic heat-bath configuration interaction methods, we obtain results that seem to be converged to full configuration interaction results within 5 kJ/mol. Our best result for ∆E is 101 kJ/mol. With this reference, we show that M06 and B3LYP-D3 give the best results among 35 DFT methods tested for this system. Brueckner doubles coupled cluster with perturbaitve triples seems to be the most accurate coupled-cluster approach with approximate triples. CCSD(T) with Kohn–Sham orbitals gives results within 4–11 kJ/mol of the extrapolated CC results, depending on the DFT method. Single-reference CC calculations seem to be reasonably accurate (giving an error of ∼5 kJ/mol compared to multireference methods), even if the D1 diagnostic is quite high (0.25) for one of the two isomers. (Less)
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author
; ; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of chemical physics
volume
159
issue
4
article number
044106
publisher
American Institute of Physics (AIP)
external identifiers
  • pmid:37486046
  • scopus:85166487652
ISSN
0021-9606
DOI
10.1063/5.0152611
language
English
LU publication?
yes
id
e80d12f2-322c-4975-a40d-02cae63fde8b
date added to LUP
2023-09-25 16:46:51
date last changed
2023-10-02 13:35:07
@article{e80d12f2-322c-4975-a40d-02cae63fde8b,
  abstract     = {{We have designed a [Fe(SH)4H]− model with the fifth proton binding either to Fe or S. We show that the energy difference between these two isomers (∆E) is hard to estimate with quantum-mechanical (QM) methods. For example, different density functional theory (DFT) methods give ∆E estimates that vary by almost 140 kJ/mol, mainly depending on the amount of exact Hartree–Fock included (0%–54%). The model is so small that it can be treated by many high-level QM methods, including coupled-cluster (CC) and multiconfigurational perturbation theory approaches. With extrapolated CC series (up to fully connected coupled-cluster calculations with singles, doubles, and triples) and semistochastic heat-bath configuration interaction methods, we obtain results that seem to be converged to full configuration interaction results within 5 kJ/mol. Our best result for ∆E is 101 kJ/mol. With this reference, we show that M06 and B3LYP-D3 give the best results among 35 DFT methods tested for this system. Brueckner doubles coupled cluster with perturbaitve triples seems to be the most accurate coupled-cluster approach with approximate triples. CCSD(T) with Kohn–Sham orbitals gives results within 4–11 kJ/mol of the extrapolated CC results, depending on the DFT method. Single-reference CC calculations seem to be reasonably accurate (giving an error of ∼5 kJ/mol compared to multireference methods), even if the D1 diagnostic is quite high (0.25) for one of the two isomers.}},
  author       = {{Vysotskiy, Victor P. and Torbjörnsson, Magne and Jiang, Hao and Larsson, Dennis and Cao, Lili and Ryde, Ulf and Zhai, Huanchen and Lee, Seunghoon and Chan, Garnet Kin-Lic}},
  issn         = {{0021-9606}},
  language     = {{eng}},
  month        = {{07}},
  number       = {{4}},
  publisher    = {{American Institute of Physics (AIP)}},
  series       = {{The Journal of chemical physics}},
  title        = {{Assessment of DFT functionals for a minimal nitrogenase [Fe(SH)4H]− model employing state-of-the-art <i>ab initio</i> methods}},
  url          = {{http://dx.doi.org/10.1063/5.0152611}},
  doi          = {{10.1063/5.0152611}},
  volume       = {{159}},
  year         = {{2023}},
}