Aspects of aqueous iron and manganese (II/III) self-exchange electron transfer reactions

Kevin M. Rosso, Dayle M.A. Smith, Michel Dupuis

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

Ab initio methods were applied to the calculation of the reorganization energy A and the electronic coupling matrix element V AB for the outer-sphere Fe(OH 2) 6 II/III and Mn(OH 2) 6 II/III self-exchange electron transfer (ET) reactions. For the Fe case, we find an appreciable effect on V AB depending on whether the minority spin electron occupies the d xy orbital or a mixture of d xz/d yz orbitals in the Fe II ion. While these two possible nearly isoenergetic electron accepting states alter the magnitude and distance dependence of V AB, they do not affect the internal reorganization energy λ I to any significant level. The magnitude and distance dependence of V AB are found to be strongly dependent on encounter orientation, as expected. V AB values for corner-to-corner encounter orientations are substantially larger at any given ET distance considered than those for face-to-face encounter orientations. Values of the decay parameter β are in good agreement with well-accepted values. The adiabaticity criterion is tied to orientation and distance dependence of V AB.

Original languageEnglish
Pages (from-to)5242-5248
Number of pages7
JournalJournal of Physical Chemistry A
Volume108
Issue number24
DOIs
Publication statusPublished - Jun 17 2004

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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