Path-integral Monte Carlo simulations for electronic dynamics on molecular chains. I. Sequential hopping and super exchange.

An improved real-time quantum Monte Carlo procedure is presented and applied to describe the electronic transfer dynamics along molecular chains. The model consists of discrete electronic sites coupled to a thermal environment which is integrated out exactly within the path integral formulation. The approach is numerically exact and its results reduce to known analytical findings (Marcus theory, golden rule) in proper limits. Special attention is paid to the role of superexchange and sequential hopping at lower temperatures in symmetric donor-bridge-acceptor systems. In contrast to previous approximate studies, superexchange turns out to play a significant role only for extremely high-lying bridges where the transfer is basically frozen or for extremely low temperatures where for weaker dissipation a description in terms of rate constants is no longer feasible. For bridges with increasing length an algebraic decrease of the yield is found for short as well as for long bridges. The approach can be extended to electronic systems with more complicated topologies including impurities and in presence of external time-dependent forces. (c) 2004 American Institute of Physics.