title: Isotopic effect and temperature dependent intramolecular excitation energy transfer in a model donor-acceptor dyad.
abstract: We consider here the non-adiabatic energy transfer dynamics for a model bi-chromophore system consisting of a perylenemonoimide unit linked to a ladder-type poly(para-phenylene) oligomer. Starting from a semi-empirical parameterization of a model electron/phonon Hamiltonian, we compute the golden-rule rate for energy transfer from the LPPP5 donor to the PMI acceptor. Our results indicate that the non-adiabatic transfer is promoted by the out-of-plane wagging modes of the C-H bonds even though theses modes give little or no contribution to the Franck-Condon factors in this system. We also predict a kinetic isotope effect of k((H))/k((D)) = 1.7-2.5 depending upon the temperature.
authors.affiliation: Department of Chemistry, University of Houston, Houston TX 77204-5003, USA.
authors.forename: Jaykrishna
authors.initials: J
authors.lastname: Singh
authors.forename: Eric R
authors.initials: ER
authors.lastname: Bittner