Abstract
The protocol put forward in the present paper 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 V5/3/I versus V. This curve exhibits two maxima: one at positive bias (V = Vp+), another at negative bias (V = Vp-). The values Vp+ > 0 and Vp- < 0 at the two peaks of the curve for V5/3/I at positive and negative bias and the corresponding values Ip+ = I(Vp+) > 0 and Ip- = I(Vp-) < 0 of the current is all information needed as input. The arithmetic average of Vp+ and |Vp-| in volt provides the value in electronvolt of the MO energy offset ε0 = EMO - EF relative to the electrode Fermi level (|ε0| = e(Vp+ + |Vp-|)/2). The value of the (Stark) strength of the bias-driven MO shift is obtained as γ = (4/5)(Vp+ - |Vp-|)/(Vp+ + |Vp-|) sign (ε0). Even the low-bias conductance estimate, G = (3/8)(Ip+/Vp+ + Ip-/Vp-), 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 σ and delocalized π electrons, and various techniques (mechanically controlled break junctions, STM break junctions, conducting probe AFM junctions, and large area junctions).
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