The main structural and electronic factors playing a role in intramolecular dissociative electron transfer of a simple donor - peptide - acceptor (D - peptide - A) model have been investigated by an integrated computational protocol based on the density functional theory, its time-dependent extension, and the polarizable continuum model. Our results allow us to elucidate the electronic states involved in the process and how they are perturbed by the orientation of the donor and the acceptor with respect to the peptide chain and by the presence of the solvent. We also report a semiquantitative estimation of the rate constant governing electron transfer obtained by a direct quantum mechanical evaluation of all the terms entering the kinetic expressions based on the Marcus theory and its extensions. © 2006 American Chemical Society.

*** IBB - CNR ***

Dipartimento di Chimica, Università Federico II, Complesso Monte S. Angela, via Cintia, 1-80126 Napoli, Italy

Brookhaven National Laboratory, Upton, NY 11973-5000, United States

Istituto di Biostrutture e Bioimmagini, CNR, via Mezzocannone 16, 80134 Napoli, Italy

University of Padua, INFN, Padua, Italy

University of Birmingham, Birmingham, United Kingdom

University of Catania, INFN, Catania, Italy

Physics Department, University of Athens, Athens, Greece

Institute of Experimental Physics, Slovak Academy of Science, Ko ice, Slovakia

Dipartiemnto IA di Fisica, Universit e del Politecnico di Bari, INFN, Bari, Italy

CERN, European Laboratory for Particle Physics, Geneva, Switzerland

University La Sapienza, INFN, Rome, Italy

State University of St. Petersburg, St. Petersburg, Russian Federation

Dipartiemnto di Scienze Fisiche E. R. Caianiello dell' Universit, INFN, Salerno, Italy

H gskolen i Bergen, Bergen, Norway

Fysisk Institutt, Universitetet i Oslo, Oslo, Norway

Utrecht University, NIKHEF, Utrecht, Netherlands

IReS, ULP, Strasbourg, France

Institutt for Fysikk og Teknologi, Universitetet i Bergen, Bergen, Norway

Coll ge de France, Paris, France

Institute of Physics, Prague, Czech Republic

P. J. af rik University, Ko ice, Slovakia

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