Author ORCID Identifier
https://orcid.org/0000-0002-2956-9781
Document Type
Article
Publication Date
9-2012
Publication Title
Journal of Computational Chemistry
Volume
34
First Page
141
Last Page
148
Abstract
The performance of a range density functional theory functionals combined in a quantum mechanical (QM)/molecular mechanical (MM) approach was investigated in their ability to reliably provide geometries, electronic distributions, and relative energies of a multicentered open‐shell mechanistic intermediate in the mechanism 8R–Lipoxygenase. With the use of large QM/MM active site chemical models, the smallest average differences in geometries between the catalytically relevant quartet and sextet complexes were obtained with the B3LYP* functional. Moreover, in the case of the relative energies between 4II and 6II, the use of the B3LYP*functional provided a difference of 0.0 kcal mol–1. However, B3LYP± and B3LYP also predicted differences in energies of less than 1 kcal mol–1. In the case of describing the electronic distribution (i.e., spin density), the B3LYP*, B3LYP, or M06‐L functionals appeared to be the most suitable. Overall, the results obtained suggest that for systems with multiple centers having unpaired electrons, the B3LYP* appears most well rounded to provide reliable geometries, electronic structures, and relative energies.
DOI
10.1002/jcc.23114
Recommended Citation
Bushnell, Eric Andre and Gauld, James. (2012). An assessment of pure, hybrid, meta, and hybrid‐meta GGA density functional theory methods for open‐shell systems: The case of the nonheme iron enzyme 8R–LOX. Journal of Computational Chemistry, 34, 141-148.
https://scholar.uwindsor.ca/chemistrybiochemistrypub/122