Theoretical study of vibrational wave-packet dynamics in electron-transfer systems

The vibrational wave-packet dynamics associated with ultrafast electron-transfer reactions in a condensed phase environment is studied. Applying the recently proposed self-consistent hybrid method to simulate the quantum dynamics of these reactions, we consider various electron-transfer systems including the spin-boson model with Debye spectral density, a reaction-coordinate model, as well as photoinduced electron-transfer reactions in a mixed valence compound. The results of the study demonstrate the interplay between electron-transfer dynamics and coherent vibrational motion of inner-sphere modes. Furthermore, the occurrence and quenching of electronic and vibrational coherence effects in electron-transfer reactions is discussed in some detail. (C) 2003 Elsevier B.V. All rights reserved.