Inner-sphere electron-transfer reorganization energies of zinc porphyrins

Xenia Amashukeli, Nadine E. Gruhn, Dennis L. Lichtenberger, Jay R. Winkler, Harry B. Gray

Research output: Contribution to journalArticle

47 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)15566-15571
Number of pages6
JournalJournal of the American Chemical Society
Volume126
Issue number47
DOIs
StatePublished - Dec 1 2004

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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