UNSPECIFIED (2005) Iron(IV) porphyrin difluoride does not exist: Implications for DFT calculations on heme protein reaction pathways. JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 1 (4). pp. 597-600. doi:10.1021/ct050086s ISSN 1549-9618.

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Abstract

DFT (133LYP as well as a number of common exchange-correlation functionals) predicts a low-spin Fe(IV) ground state for Fe(P)F-2 (P = porphyrinato), whereas electrochemical evidence has apparently indicated an Fe(III) porphyrin pi-cation radical formulation for such a species. Ab initio CASPT2 calculations favor a high-spin porphyrin g-cation radical as the ground state by a significant energetic margin, thus dramatically overturning the DFT results. In contrast, both DFT and CASPT2 calculations correctly indicate a true Mn(IV) ground state for Mn(P)F-2. The remarkable failure of DFT to correctly predict the metal- versus ligand-oxidized nature of Fe(P)F-2 may have significant ramifications for the theoretical modeling of heme protein reaction pathways where until now the performance of DFT has raised little concern.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry Q Science > QC Physics
Journal or Publication Title:	JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Publisher:	AMER CHEMICAL SOC
ISSN:	1549-9618
Official Date:	July 2005
Dates:	Date Event July 2005 UNSPECIFIED
Volume:	1
Number:	4
Number of Pages:	4
Page Range:	pp. 597-600
DOI:	10.1021/ct050086s
Publication Status:	Published

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