Amashukeli, Xenia and Gruhn, Nadine E. and Lichtenberger, Dennis L. and Winkler, Jay R. and Gray, Harry B. (2004) Inner-Sphere Electron-Transfer Reorganization Energies of Zinc Porphyrins. Journal of the American Chemical Society, 126 (47). pp. 15566-15571. ISSN 0002-7863. doi:10.1021/ja0351037. https://resolver.caltech.edu/CaltechAUTHORS:20170425-073409553
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Abstract
Inner-sphere electron-transfer reorganization energies of Zn(protoporphyrin IX) and Zn(octaethylporphyrin) are determined from band-shape analyses of the first ionization obtained by gas-phase valence photoelectron spectroscopy. The experimentally determined total inner-sphere reorganization energies for self-exchange (120−140 meV) indicate that structural changes upon oxidation are largely confined to the porphyrin ring, and substituents on the ring or solvent and other environmental factors make smaller contributions. Computational estimates by different models vary over a wide range and are sensitive to numerical precision factors for these low reorganization energies. Of current computational models that are widely available and practical for molecules of this size, functionals that contain a mixture of Hartree−Fock exchange and DFT exchange-correlation appear to be the most applicable.
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| Additional Information: | © 2004 American Chemical Society. Received March 11, 2003. Publication Date (Web): November 5, 2004. We thank F. Ann Walker for providing the sample of Zn(oep). This work was supported by the NSF (CHE-0078809, H.B.G., J.R.W.; CHE-0078457, D.L.L.) and the DOE (DE-FG03-95ER14574, D.L.L.). | |||||||||
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| Issue or Number: | 47 | |||||||||
| DOI: | 10.1021/ja0351037 | |||||||||
| Record Number: | CaltechAUTHORS:20170425-073409553 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20170425-073409553 | |||||||||
| Official Citation: | Inner-Sphere Electron-Transfer Reorganization Energies of Zinc Porphyrins Xenia Amashukeli, Nadine E. Gruhn, Dennis L. Lichtenberger, Jay R. Winkler, and Harry B. Gray Journal of the American Chemical Society 2004 126 (47), 15566-15571 DOI: 10.1021/ja0351037 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 76895 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Tony Diaz | |||||||||
| Deposited On: | 25 Apr 2017 16:35 | |||||||||
| Last Modified: | 15 Nov 2021 17:03 |
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