Orbital Alignment as a Key Determinant of Nanotransport in Molecular Tunnel Junctions Despite Fermi Level Pinning: Exponential Correlation with Molecule–Electrode Coupling

At first glance, interrogating the impact of molecular orbital alignment on charge transport in molecular tunnel junctions may appear out of place, given the well-documented strong Fermi level pinning effect. To demonstrate that the contrary is true, we investigated molecular junctions based on self-assembled monolayers (SAMs) of alkyl monothiols (CnT) and dithiols (CnDT) with Ag, Au, and Pt electrodes using the conducting probe atomic force microscopy (CP-AFM) platform. Analysis of these data reveals that the HOMO–metal electronic coupling Γ and the low bias conductance G are exponentially correlated with the HOMO energy offset relative to the Fermi level ε₀ = E_MO – E_F (Γ ∝ exp(−α̅|ε₀|), G ∝ exp(−α|ε₀|), α ≈ 2α̅). This impact is remarkably strong: for CnT junctions, a reduction by only 25% in |ε₀| translates into an increase of Γ by 1 order of magnitude and of G by 2 orders of magnitude. More broadly, this exponential correlation of Γ and G with ε₀ offers deeper insight into nanotransport and extends understanding of the previously reported exponential dependence of Γ and G on the SAM-induced work function shift ΔΦ, which reflects the linear correlation between ε₀ and ΔΦ. From a fundamental perspective, it is crucial to highlight that our data validate a formula for Γ (a property which depends on both electrodes of a junction), which features (i) ε₀ rather than ΔΦ (i.e., a property of a full junction versus a property of a “half a junction”) and (ii) ε₀ rather than its square root in the exponent, thereby invalidating the widely employed tunneling barrier picture.