Comparison of the accuracy of DFT methods for reactions with relevance to nitrogenase
Torbjörnsson, Magne LU and Ryde, Ulf LU
(2021)
In Electronic Structure
3(3).
- Abstract
We have studied the accuracy of 16 different density functional theory methods to reproduce experimental data for bond lengths, angles, vibrational frequencies, as well as enthalpies and entropies for the binding of N2, H2, CO and hydride ions to various transition-metal complexes (with Fe, Ni, Cr, Mo andW) with relation to nitrogenase.We show that generalized gradient approximation functionals give better structure-related parameters, whereas hybrid functionals often give better energies. However, the BLYP and B97D functionals seem to give reasonably accurate results for both types of properties. Geometries and entropies are converged with split-valence basis sets, but energies and vibrational frequencies (and therefore also thermal... (More)
We have studied the accuracy of 16 different density functional theory methods to reproduce experimental data for bond lengths, angles, vibrational frequencies, as well as enthalpies and entropies for the binding of N2, H2, CO and hydride ions to various transition-metal complexes (with Fe, Ni, Cr, Mo andW) with relation to nitrogenase.We show that generalized gradient approximation functionals give better structure-related parameters, whereas hybrid functionals often give better energies. However, the BLYP and B97D functionals seem to give reasonably accurate results for both types of properties. Geometries and entropies are converged with split-valence basis sets, but energies and vibrational frequencies (and therefore also thermal corrections) in general require a basis set of triple-zeta quality. Dispersion corrections are important to obtain accurate energies (contributing by up to 57 kJ mol-1), as well as structures.
(Less)
- author
- Torbjörnsson, Magne
LU
and Ryde, Ulf
LU
- organization
- publishing date
- 2021-09
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- Density functional theory, Dispersion, Hartree-Fock exchange, Nitrogenase models, Thermal corrections
- in
- Electronic Structure
- volume
- 3
- issue
- 3
- article number
- 034005
- publisher
- IOP Publishing
- external identifiers
-
- scopus:85115448968
- ISSN
- 2516-1075
- DOI
- 10.1088/2516-1075/ac1a63
- language
- English
- LU publication?
- yes
- id
- 2648b4cc-77d6-4b2f-a575-3cdb22aa699c
- date added to LUP
- 2021-10-06 22:56:29
- date last changed
- 2023-04-02 17:59:19
@article{2648b4cc-77d6-4b2f-a575-3cdb22aa699c,
abstract = {{<p>We have studied the accuracy of 16 different density functional theory methods to reproduce experimental data for bond lengths, angles, vibrational frequencies, as well as enthalpies and entropies for the binding of N2, H2, CO and hydride ions to various transition-metal complexes (with Fe, Ni, Cr, Mo andW) with relation to nitrogenase.We show that generalized gradient approximation functionals give better structure-related parameters, whereas hybrid functionals often give better energies. However, the BLYP and B97D functionals seem to give reasonably accurate results for both types of properties. Geometries and entropies are converged with split-valence basis sets, but energies and vibrational frequencies (and therefore also thermal corrections) in general require a basis set of triple-zeta quality. Dispersion corrections are important to obtain accurate energies (contributing by up to 57 kJ mol-1), as well as structures. </p>}},
author = {{Torbjörnsson, Magne and Ryde, Ulf}},
issn = {{2516-1075}},
keywords = {{Density functional theory; Dispersion; Hartree-Fock exchange; Nitrogenase models; Thermal corrections}},
language = {{eng}},
number = {{3}},
publisher = {{IOP Publishing}},
series = {{Electronic Structure}},
title = {{Comparison of the accuracy of DFT methods for reactions with relevance to nitrogenase}},
url = {{http://dx.doi.org/10.1088/2516-1075/ac1a63}},
doi = {{10.1088/2516-1075/ac1a63}},
volume = {{3}},
year = {{2021}},
}