The accuracy of geometries for iron porphyrin complexes from density functional theory
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The accuracy of geometries for iron porphyrin complexes from density functional theory. / Rydberg, Patrik Åke Anders; Olsen, Lars.
I: Journal of Physical Chemistry A, Bind 113, Nr. 43, 2009, s. 11949-11953.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - The accuracy of geometries for iron porphyrin complexes from density functional theory
AU - Rydberg, Patrik Åke Anders
AU - Olsen, Lars
N1 - Keywords: Crystallography, X-Ray; Iron; Ligands; Metalloporphyrins; Models, Molecular; Molecular Conformation; Oxidation-Reduction; Quantum Theory
PY - 2009
Y1 - 2009
N2 - Iron porphyrin complexes are cofactors in many important proteins such as cytochromes P450, hemoglobin, heme peroxidases, etc. Many computational studies on these systems have been done over the past decade. In this study, the performance of some of the most commonly used density functional theory functionals is evaluated with regard to how they reproduce experimental structures. Seven different functionals (BP86, PBE, PBE0, TPSS, TPSSH, B3LYP, and B97-D) are used to study eight different iron porphyrin complexes. The results show that the TPSSH, PBE0, and TPSS functionals give the best results (absolute bond distance deviations of 0.015-0.016 A), but the geometries are well-reproduced by all functionals except B3LYP. We also test four different basis sets of double-zeta quality, and we find that a combination of double-zeta basis set of Schafer et al. on the iron atom and the 6-31G* basis set on the other atoms performs best. Finally, we remove the porphyrin side chains and increase the basis set size systematically to see if this affects the results. We show that basis sets larger than double-zeta quality are not necessary to get accurate geometries, and nonaromatic side chains do not affect the geometries.
AB - Iron porphyrin complexes are cofactors in many important proteins such as cytochromes P450, hemoglobin, heme peroxidases, etc. Many computational studies on these systems have been done over the past decade. In this study, the performance of some of the most commonly used density functional theory functionals is evaluated with regard to how they reproduce experimental structures. Seven different functionals (BP86, PBE, PBE0, TPSS, TPSSH, B3LYP, and B97-D) are used to study eight different iron porphyrin complexes. The results show that the TPSSH, PBE0, and TPSS functionals give the best results (absolute bond distance deviations of 0.015-0.016 A), but the geometries are well-reproduced by all functionals except B3LYP. We also test four different basis sets of double-zeta quality, and we find that a combination of double-zeta basis set of Schafer et al. on the iron atom and the 6-31G* basis set on the other atoms performs best. Finally, we remove the porphyrin side chains and increase the basis set size systematically to see if this affects the results. We show that basis sets larger than double-zeta quality are not necessary to get accurate geometries, and nonaromatic side chains do not affect the geometries.
KW - Former Faculty of Pharmaceutical Sciences
U2 - 10.1021/jp9035716
DO - 10.1021/jp9035716
M3 - Journal article
C2 - 19663404
VL - 113
SP - 11949
EP - 11953
JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
SN - 1089-5639
IS - 43
ER -
ID: 17655569