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The Theory of Long Distance Electron Transfer Reactions


Beratan, David Nathan (1986) The Theory of Long Distance Electron Transfer Reactions. Dissertation (Ph.D.), California Institute of Technology.


The rate of electron transport between distant sites was studied. The rate depends crucially on the chemical details of the donor, acceptor, and surrounding medium. These reactions involve electron tunneling through the intervening medium and are, therefore, profoundly influenced by the geometry and energetics of the intervening molecules. The dependence of rate on distance was considered for several rigid donor-acceptor "linkers" of experimental importance. Interpretation of existing experiments and predictions for new experiments were made.

The electronic and nuclear motion in molecules is correlated. A Born-Oppenheimer separation is usually employed in quantum chemistry to separate this motion. Long distance electron transfer rate calculations require the total donor wave function when the electron is very far from its binding nuclei. The Born-Oppenheimer wave functions at large electronic distance are shown to be qualitatively wrong. A model which correctly treats the coupling was proposed. The distance and energy dependence of the electron transfer rate was determined for such a model.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Marcus, Rudolph A.
Thesis Committee:
  • Marcus, Rudolph A. (chair)
  • Hopfield, John J.
  • Gray, Harry B.
  • Dervan, Peter B.
Defense Date:11 June 1985
Funding AgencyGrant Number
Record Number:CaltechTHESIS:04012014-082222627
Persistent URL:
Beratan, David Nathan0000-0003-4758-8676
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:8175
Deposited By: John Wade
Deposited On:01 Apr 2014 17:05
Last Modified:10 Aug 2018 20:19

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