Isotopic Effect and Temperature Dependent Intramolecular Excitation Energy Transfer in a Model Donor-Acceptor Dyad

TL;DR

This study models the non-adiabatic energy transfer in a donor-acceptor dyad, revealing the influence of vibrational modes and predicting a significant isotope effect dependent on temperature.

Contribution

It introduces a semi-empirical model for energy transfer dynamics in a bi-chromophore system, highlighting the role of out-of-plane vibrational modes and isotope effects.

Findings

Out-of-plane wagging modes promote energy transfer.

Predicted kinetic isotope effect of 1.7-2.5 depending on temperature.

Non-adiabatic transfer is influenced by specific vibrational modes.

Abstract

We consider here the non-adiabatic energy transfer dynamics for a model bi-chromophore system consisting of a perylenediimide 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 PDI 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.