These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
3 files

Towards a First-Principles Evaluation of Transport Mechanisms in Molecular Wires

submitted on 27.06.2020, 14:59 and posted on 30.06.2020, 05:11 by Susanne kröncke, Carmen Herrmann
Understanding charge transport through molecular wires is important for nanoscale electronics and biochemistry. Our goal is to establish a simple first-principles protocol for predicting the charge transport mechanism in such wires, in particular the crossover from coherent tunneling for short wires to incoherent hopping for longer wires. This protocol is based on a combination of density-functional theory with a polarizable continuum model introduced by Kaupp et al. for mixed-valence molecules, which we had previously found to work well for length-dependent charge delocalization in such systems. We combine this protocol with a new charge delocalization measure tailored for molecular wires, and we show that it can predict the tunneling-to hopping transition length with a maximum error of one subunit in five sets of molecular wires studied experimentally in molecular junctions at room temperature. This suggests that the protocol is also well suited for estimating the extent of hopping sites as relevant, e.g., for the intermediate tunneling-hopping regime in DNA.


DFG HE 5675/4-1

Pro Exzellenzia 4.0


Email Address of Submitting Author


University of Hamburg



ORCID For Submitting Author


Declaration of Conflict of Interest