Intramolecular electron transfer theory: A study of purely electronic effects

Site-to-site electron and hole migration is studied in two- and three-site Hubbard systems, employing the propagator method. Time-dependent transfer probabilities are calculated. The effects of orbital coupling and single-site transfer probability are discussed. The effect of basis function overlap on the site-to-site transfer probability in a two-site Hubbard system is studied. The relationship between the rate constant obtained from a correlation function method and a time-dependent transfer probability expression is discussed. A time-dependent number operator is derived from the correlation function expression. The vibronic nature of intramolecular electron transfer is also discussed. Preliminary numerical results for ruthenium systems are reported.