### Abstract

The dynamical formulation of electron transfer rate theory, including inner sphere and outer sphere reorganization terms, electronic structure polarization, and an ab initio treatment of the electrons on donor, acceptor, and bridge molecules, is presented and applied to electron transfer betwen benzene/anion radical and pyridine. The formulation involves the use of mean field (Ehrenfest) relations to obtain the time evolution of electron and vibration operators. This formulation yields an effective density matrix for the time evolution of the electronic system; the elements of this density matrix depend on averages over electronic and vibrational motions. For the electron transfer system actually studied, the rates are strongly dependent upon relative geometry of donor and acceptor, and maximize sharply at geometries such that electronic levels on donor and acceptor become degenerate - the so-called "coincidence event" geometry.

Original language | English |
---|---|

Pages (from-to) | 4237-4247 |

Number of pages | 11 |

Journal | Journal of Chemical Physics |

Volume | 90 |

Issue number | 8 |

Publication status | Published - 1989 |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

*Journal of Chemical Physics*,

*90*(8), 4237-4247.

**Dynamical theory of electron transfer : Inclusion of inner-shell reorganization.** / Mikkelsen, K. V.; Ratner, Mark A.

Research output: Contribution to journal › Article

*Journal of Chemical Physics*, vol. 90, no. 8, pp. 4237-4247.

}

TY - JOUR

T1 - Dynamical theory of electron transfer

T2 - Inclusion of inner-shell reorganization

AU - Mikkelsen, K. V.

AU - Ratner, Mark A

PY - 1989

Y1 - 1989

N2 - The dynamical formulation of electron transfer rate theory, including inner sphere and outer sphere reorganization terms, electronic structure polarization, and an ab initio treatment of the electrons on donor, acceptor, and bridge molecules, is presented and applied to electron transfer betwen benzene/anion radical and pyridine. The formulation involves the use of mean field (Ehrenfest) relations to obtain the time evolution of electron and vibration operators. This formulation yields an effective density matrix for the time evolution of the electronic system; the elements of this density matrix depend on averages over electronic and vibrational motions. For the electron transfer system actually studied, the rates are strongly dependent upon relative geometry of donor and acceptor, and maximize sharply at geometries such that electronic levels on donor and acceptor become degenerate - the so-called "coincidence event" geometry.

AB - The dynamical formulation of electron transfer rate theory, including inner sphere and outer sphere reorganization terms, electronic structure polarization, and an ab initio treatment of the electrons on donor, acceptor, and bridge molecules, is presented and applied to electron transfer betwen benzene/anion radical and pyridine. The formulation involves the use of mean field (Ehrenfest) relations to obtain the time evolution of electron and vibration operators. This formulation yields an effective density matrix for the time evolution of the electronic system; the elements of this density matrix depend on averages over electronic and vibrational motions. For the electron transfer system actually studied, the rates are strongly dependent upon relative geometry of donor and acceptor, and maximize sharply at geometries such that electronic levels on donor and acceptor become degenerate - the so-called "coincidence event" geometry.

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UR - http://www.scopus.com/inward/citedby.url?scp=36549101898&partnerID=8YFLogxK

M3 - Article

VL - 90

SP - 4237

EP - 4247

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 8

ER -