کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1317411 | 976531 | 2006 | 6 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: DFT and the electromerism in complexes of iron with diatomic ligands DFT and the electromerism in complexes of iron with diatomic ligands](/preview/png/1317411.png)
A reliable procedure is proposed for assigning the electronic structures for large biologically-relevant systems, where the size of the model confines one to the use of density functional theory (DFT) methods, and where the risk of over-interpreting DFT-derived molecular orbitals and spin densities still exists. The proposed approach focuses on the use of the only DFT-derived parameter that is unanimously recognized to be reliable: the geometry. We examine DFT-derived O–O bond lengths in formally ferrous-dioxygen models, and compare them to bond lengths in free, non metal-bound, dioxygen, superoxide and peroxide moieties. Likewise, we compare the N–O bond lengths within ferrous-nitrosyl {FeNO}7 models, with the same parameter in free NO+, NO, and HNO species. This allows a calibrated, straightforward way of assigning the electronic structure in systems where electromerism makes detailed single-reference molecular orbital analysis unreliable.
Journal: Journal of Inorganic Biochemistry - Volume 100, Issue 1, January 2006, Pages 161–166