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Iron(IV) porphyrin difluoride does not exist: Implications for DFT calculations on heme protein reaction pathways
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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
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Official URL: http://dx.doi.org/10.1021/ct050086s
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 | ||||
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| Subjects: | Q Science > QD Chemistry Q Science > QC Physics |
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| Journal or Publication Title: | JOURNAL OF CHEMICAL THEORY AND COMPUTATION | ||||
| Publisher: | AMER CHEMICAL SOC | ||||
| ISSN: | 1549-9618 | ||||
| Official Date: | July 2005 | ||||
| Dates: |
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| Volume: | 1 | ||||
| Number: | 4 | ||||
| Number of Pages: | 4 | ||||
| Page Range: | pp. 597-600 | ||||
| DOI: | 10.1021/ct050086s | ||||
| Publication Status: | Published |
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