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Not innocent : verdict from ab initio multiconfigurational second-order perturbation theory on the electronic structure of chloroiron corrole

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Roos, Bjorn O., Veryazov, Valera, Conradie, Jeanet, Taylor, Peter R. (Peter Robert) and Ghosh, Abhik. (2008) Not innocent : verdict from ab initio multiconfigurational second-order perturbation theory on the electronic structure of chloroiron corrole. The Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical, Vol.112 (No.45). pp. 14099-14102. ISSN 1520-6106

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Abstract

From a suitably broad perspective, transition metal corroles may be viewed as stable, synthetic analogues of high-valent heme protein intermediates such as compounds I and II. Against this backdrop, the electronic structure of chloroiron corrole has provoked a lively debate in recent years. Thus, whereas NMR spectroscopy and DFT calculations suggest an S = 3/2 Fe(III) corrole(center dot 2-) radical description, certain researchers have favored an Fe(IV) formulation. These two descriptions are indistinguishable as far as DFT calculations are concerned. Ab initio CASSCF/CASPT2 calculations provide unambiguous support for the former description. In addition, they rule out any Fe(IV) state, whether high- or low-spin, within 1.5 eV of the ground state.

Item Type: Journal Article
Subjects: Q Science > QA Mathematics
Q Science > QD Chemistry
Divisions: Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH): Perturbation (Mathematics), Density functionals
Journal or Publication Title: The Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical
Publisher: American Chemical Society
ISSN: 1520-6106
Official Date: 13 November 2008
Volume: Vol.112
Number: No.45
Number of Pages: 4
Page Range: pp. 14099-14102
Identification Number: 10.1021/jp807734x
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Restricted or Subscription Access
Funder: Royal Society (Great Britain), Norges forskningsråd [Norwegian Research Council], Sweden. Vetenskapsrådet [Swedish Research Council], Wolfson Foundation
References:

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URI: http://wrap.warwick.ac.uk/id/eprint/29073

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