Gaining insight into molecular tunnel junctions with a pocket calculator without I-V data fitting. Five-thirds protocol

The proposed protocol is an attempt to meet the experimentalists' legitimate desire of reliably and easily extracting microscopic parameters from current-voltage measurements on molecular junctions. It applies to junctions wherein charge transport dominated by a single level (molecular orbital, MO) occurs via off-resonant tunneling. The recipe is simple. The measured current-voltage curve $I = I(V)$ should be recast as a curve of $V^{5/3}/I$ versus $V$. This curve exhibits two maxima: one at positive bias ($V = V_{p+}$), another at negative bias ($V = V_{p-}$). The values $V_{p +} > 0$ and $V_{p -} < 0$ at the two peaks of the curve for $V^{5/3}/I$ at positive and negative bias and the corresponding values $I_{p +} = I(V_{p+}) > 0$ and $I_{p -} = I(V_{p-}) < 0$ of the current is all information needed as input. The arithmetic average of $V_{p +}$ and $\vert V_{p -}\vert$ in volt provides the value in electronvolt of the MO energy offset $\varepsilon_0 = E_{MO} - E_F$ relative to the electrode Fermi level ($\vert \varepsilon_0\vert = e (V_{p +} + \vert V_{p -}\vert )/2$). The value of the (Stark) strength of the bias-driven MO shift is obtained as $\gamma = (4/5) (V_{p +} - \vert V_{p -} \vert) / (V_{p +} + \vert V_{p -} \vert)$. Even the low-bias conductance estimate, $G = (3/8) (I_{p +} / V_{p +} + I_{p -} / V_{p -})$, can be a preferable alternative to that deduced from fitting the $I$-$V$ slope in situations of noisy curves at low bias. To demonstrate the reliability and the generality of this ``five-thirds'' protocol, I illustrate its wide applicability for molecular tunnel junctions fabricated using metallic and nonmetallic electrodes, molecular species possessing localized $\sigma$ and delocalized $\pi$ electrons, and} various techniques (mechanically controlled break junctions, STM break junctions, conducting probe AFM junctions, and large area junctions).