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Not Innocent: Verdict from Ab Initio Multiconfigurational Second-Order Perturbation Theory on the Electronic Structure of Chloroiron Corrole

Roos, Björn LU ; Veryazov, Valera LU ; Conradie, Jeanet; Taylor, Peter R. and Ghosh, Abhik (2008) In The Journal of Physical Chemistry Part B 112(45). p.14099-14102
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... (More)
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. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part B
volume
112
issue
45
pages
14099 - 14102
publisher
The American Chemical Society
external identifiers
  • wos:000260675800003
  • scopus:57149085901
ISSN
1520-5207
DOI
10.1021/jp807734x
language
English
LU publication?
yes
id
bc030974-a29d-4ea5-9338-2d727ddf84bc (old id 1283083)
date added to LUP
2009-02-10 11:59:22
date last changed
2017-11-05 03:59:42
@article{bc030974-a29d-4ea5-9338-2d727ddf84bc,
  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.},
  author       = {Roos, Björn and Veryazov, Valera and Conradie, Jeanet and Taylor, Peter R. and Ghosh, Abhik},
  issn         = {1520-5207},
  language     = {eng},
  number       = {45},
  pages        = {14099--14102},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Not Innocent: Verdict from Ab Initio Multiconfigurational Second-Order Perturbation Theory on the Electronic Structure of Chloroiron Corrole},
  url          = {http://dx.doi.org/10.1021/jp807734x},
  volume       = {112},
  year         = {2008},
}