Not Innocent: Verdict from Ab Initio Multiconfigurational Second-Order Perturbation Theory on the Electronic Structure of Chloroiron Corrole
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/1283083
- author
- Roos, Björn
LU
; Veryazov, Valera
LU
; Conradie, Jeanet ; Taylor, Peter R. and Ghosh, Abhik
- organization
- publishing date
- 2008
- 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}}, }