Long-Range Nonequilibrium Coherent Tunneling Induced by Fractional Vibronic Resonances

We study the influence of a linear energy bias on a nonequilibrium excitation on a chain of molecules coupled to local vibrations (a tilted Holstein model) using both a random-walk rate kernel theory and a nonperturbative, massively parallelized adaptive-basis algorithm. We uncover structured and discrete vibronic resonance behavior fundamentally different from both linear response theory and homogeneous polaron dynamics. Remarkably, resonance between the phonon energy ℏω and the bias δ_ϵ occurs not only at integer but also fractional ratios δ_ϵ/(ℏω) = m/n, which effect long-range n-bond m-phonon tunneling. These observations are reproduced in a model calculation of a recently demonstrated Cy3 system, and the effect of dipole-dipole-type non-nearest-neighbor coupling and vibrationally relaxed initial states is also considered. Potential applications range from molecular electronics to optical lattices and artificial light harvesting via vibronic engineering of coherent quantum transport.