Cooperative effects in molecular conduction

TL;DR

This study uses a tight binding model to analyze how intermolecular interactions influence molecular conduction, revealing conditions under which conduction scales linearly with molecular number and explaining conflicting experimental observations.

Contribution

It provides an exact solution framework for understanding conduction in molecular systems, incorporating both direct and through-metal interactions, and clarifies scaling behaviors.

Findings

Linear scaling of conduction with number of molecules in layers

Significant variation in conduction per molecule compared to isolated molecules

Linear scaling emerges only beyond certain molecular island sizes

Abstract

Current experimental and theoretical studies on the effect of intermolecular interactions on molecular conduction appear to be in conflict with each other. In particular, some experimental results, e.g., the observation of 2-dimensional free-particle character for interface bound electrons indicate strong intermolecular interactions while other observations indicate an additive character of conduction properties. In this paper we use a generic tight binding model with a physically motivated choice of parameters in order to examine this issue. The model encompasses direct intermolecular interactions as well as through-metal interactions and can be solved exactly to yield spectral properties (surface density of states) and transport characteristics (transmission coefficients and current-voltage behaviors) for single molecule junctions, molecular islands and molecular layers. We find linear scaling of conduction properties with the number of conducting molecules in junctions characterized by molecular layers when the probe (STM tip) addresses different numbers of molecules; however, the conduction per molecule can differ significantly from that of an isolated single molecule. When a junction involves finite molecular islands of varying sizes, linear scaling sets in only beyond a certain molecular island size, of the order of a few tens of molecules. Implications for current observation of linear scaling behaviors are discussed.