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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 orcid ; 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
; ; ; and
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 (ACS)
external identifiers
  • wos:000260675800003
  • scopus:57149085901
  • pmid:18950087
ISSN
1520-5207
DOI
10.1021/jp807734x
language
English
LU publication?
yes
additional info
The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
id
bc030974-a29d-4ea5-9338-2d727ddf84bc (old id 1283083)
date added to LUP
2016-04-01 13:35:29
date last changed
2023-04-06 09:27:21
@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 (ACS)}},
  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}},
  doi          = {{10.1021/jp807734x}},
  volume       = {{112}},
  year         = {{2008}},
}