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

Fingerprint

Manganese
manganese
electron transfer
Iron
encounters
iron
Electrons
orbitals
Electron energy levels
minorities
electron states
internal energy
electron spin
Ions
decay
matrices
electronics
ions
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Aspects of aqueous iron and manganese (II/III) self-exchange electron transfer reactions. / Rosso, Kevin M.; Smith, Dayle M A; Dupuis, Michel.

In: Journal of Physical Chemistry A, Vol. 108, No. 24, 17.06.2004, p. 5242-5248.

Research output: Contribution to journalArticle

@article{d3b74a3315f24ef8ac63523a5a51ee03,
title = "Aspects of aqueous iron and manganese (II/III) self-exchange electron transfer reactions",
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.",
author = "Rosso, {Kevin M.} and Smith, {Dayle M A} and Michel Dupuis",
year = "2004",
month = "6",
day = "17",
doi = "10.1021/jp037470a",
language = "English",
volume = "108",
pages = "5242--5248",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "24",

}

TY - JOUR

T1 - Aspects of aqueous iron and manganese (II/III) self-exchange electron transfer reactions

AU - Rosso, Kevin M.

AU - Smith, Dayle M A

AU - Dupuis, Michel

PY - 2004/6/17

Y1 - 2004/6/17

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=3042642758&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=3042642758&partnerID=8YFLogxK

U2 - 10.1021/jp037470a

DO - 10.1021/jp037470a

M3 - Article

VL - 108

SP - 5242

EP - 5248

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 24

ER -