Multi-set matrix product state calculations reveal mobile Franck-Condon excitations under strong Holstein-type coupling

Abstract

We show that the dynamics of (vertical) Franck-Condon excitations in the regime where Holstein-coupled vibrational modes mix strongly with electronic degrees of freedom sharply contrasts with the known self-localized behavior of vibrationally relaxed excitations. Instead, the strongly-coupled modes are found to periodically induce resonances between interacting electronic sites, during which effective excitation transfer occurs, allowing Franck-Condon excitations to attain substantial mean square displacements under conditions where relaxed excitations are essentially trapped to a single site. In demonstrating this behavior, we employ a multi-set matrix product state formalism. We find this numerically exact technique to be a remarkably efficient approach to the notoriously difficult problem posed by the Holstein model in the regime where the electronic coupling, the vibrational quantum, and the vibrational reorganization energy are comparable in magnitude.