Counterintuitive issues in the charge transport through molecular junctions

TL;DR

This paper challenges common assumptions in modeling charge transport through molecular junctions, revealing that typical analytical methods can misestimate key parameters and exhibit counter-intuitive behaviors not predicted by simple models.

Contribution

It demonstrates the failure of cubic expansion methods in analyzing I-V curves and shows that molecular orbital energy shifts can behave unexpectedly, questioning standard interpretative approaches.

Findings

Cubic expansions underestimate b5_0 by about a factor of two.

Model parameters depend on the bias range used for fitting.

MO energy shifts can oppose the electrode's Fermi energy change.

Abstract

Whether at phenomenological or microscopic levels, most theoretical approaches to charge transport through molecular junctions postulate or attempt to justify microscopically the existence of a dominant molecular orbital (MO). Within such single level descriptions, experimental current-voltage I-V curves are sometimes/often analyzed by using analytical formulas expressing the current as a cubic expansion in terms of the applied voltage V, and relate possible V-driven shifts of the level energy offset relative to the metallic Fermi energy \varepsilon_{0} to an asymmetry of molecule-electrode couplings or to an asymmetric location of the "center of gravity" of the MO with respect to electrodes. In this paper, we present results demonstrating the failure of these intuitive expectations. For example, we show how typical data processing based on cubic expansions yields a value of \varepsilon_0 underestimated by a typical factor of about two. When compared to theoretical results of DFT approaches, which typically underestimate the HOMO-LUMO gap by a similar factor, this may create the false impression of "agreement" with experiments in situations where this is actually not the case. Further, such cubic expansions yield model parameter values dependent on the bias range width employed for fitting, which is unacceptable physically. Finally, we present an example demonstrating that, counter-intuitively, the bias-induced change in the energy of an MO located much closer to an electrode can occur in a direction that is opposite to the change in the Fermi energy of that electrode. This is contrary to what one expects based on a "lever rule" argument, according to which the MO "feels" the local value of the electric potential, which is assumed to vary linearly across the junction and is closer to the potential of the closer electrode.