Coherent vibrational energy transfer along a peptide helix

Abstract

To measure the transport of vibrational energy along a peptide helix, Hamm and co-workers [J. Phys. Chem. B 112, 9091 (2008)] performed time-resolved vibrational experiments, which showed that the energy transport rate increases by at least a factor of 4, when a localized C=O mode of the peptide instead of an attached chromophore is excited. This finding raises the question if coherent excitonic energy transfer between the C=O modes may be of importance for the overall energy transport in peptides. With this idea in mind, nonequilibrium molecular dynamics simulations as well as quantum-classical calculations are performed, which qualitatively reproduce the experimental findings. Moreover, the latter model (an exciton Hamiltonian whose matrix elements depend on the instantaneous positions of the peptide and solvent atoms) indeed exhibits the signatures of coherent quantum energy transport, at least within the first few picoseconds and at low temperatures. The origin of the observed decoherence, the absence of vibrational self-trapping, and the possibility of quantum interference between various transport paths are discussed in some detail.