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HAL-ENS-LYON
Article . 2011
Data sources: HAL-ENS-LYON
image/svg+xml Jakob Voss, based on art designer at PLoS, modified by Wikipedia users Nina and Beao Closed Access logo, derived from PLoS Open Access logo. This version with transparent background. http://commons.wikimedia.org/wiki/File:Closed_Access_logo_transparent.svg Jakob Voss, based on art designer at PLoS, modified by Wikipedia users Nina and Beao
HAL-CEA
Article . 2011
Data sources: HAL-CEA
Journal of Chemical Theory and Computation
Article . 2011 . Peer-reviewed
Data sources: Crossref
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Toward Reliable DFT Investigations of Mn-Porphyrins through CASPT2/DFT Comparison

Authors: Kepenekian, Mikaël; Calborean, Adrian; Vetere, Valentina; Le Guennic, Boris; Robert, Vincent; Maldivi, Pascale;

Toward Reliable DFT Investigations of Mn-Porphyrins through CASPT2/DFT Comparison

Abstract

The low-energy spectroscopies of Mn(II) and Mn(III) porphyrin (P) complexes were investigated using complete active space and subsequent perturbative treatment (CASPT2) as well as DFT-based calculations. Starting from DFT optimizations of Mn(II)P and Mn(III)PCl using crystallographic data, the CASPT2 results show that whatever the relative position of the Mn(II) ion with respect to the porphyrin cavity, the high-spin state S = 5/2 of the [MnP] unit lies much lower in energy than the intermediate S = 3/2 state. Not only are these results in agreement with experimental observations but they also differ from previous theoretical conclusions. In the Mn(III) complexes, σ and π charge redistributions compete to result in a S = 2 ground state. The performances of different functionals have been tested in the reproduction of the CASPT2 spin gaps. Our results confirm that the Mn(II) system is very challenging, as GGA functionals fail in the spin states ordering and in the reproduction of the gaps, unless a high percentage of exact HF exchange (55%), as in KMLYP, is incorporated. This inspection demonstrates the need for specific active space functional to investigate the low-energy spectroscopy of [MnP] units.

Country
France
Keywords

[CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
29
Top 10%
Average
Top 10%
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