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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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Official URL: http://dx.doi.org/10.1021/jp807734x

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

Dates:

Date	Event
13 November 2008	Published

Volume:

Vol.112

Number:

No.45

Number of Pages:

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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