American Chemical Society
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Assessing the Reversed Exponential Decay of the Electrical Conductance in Molecular Wires: The Undeniable Effect of Static Electron Correlation

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journal contribution
posted on 2019-09-20, 13:36 authored by Sara Gil-Guerrero, Ángeles Peña-Gallego, Nicolás Ramos-Berdullas, Ángel Martín Pendás, Marcos Mandado
An extraordinary new family of molecular junctions, inaccurately referred to as “anti-Ohmic” wires in the recent literature, has been proposed based on theoretical predictions. The unusual electron transport observed for these systems, characterized by a reversed exponential decay of their electrical conductance, might revolutionize the design of molecular electronic devices. This behavior, which has been associated with intrinsic diradical nature, is reexamined in this work. Since the diradical character arises from a near-degeneracy of the frontier orbitals, the employment of a multireference approach is mandatory. CASSCF calculations on a set of nanowires based on polycyclic aromatic hydrocarbons (PAHs) demonstrate that, in the frame of an appropriate multireference treatment, the ground state of these systems shows the expected exponential decay of the conductance. Interestingly, these calculations do evidence a reversed exponential decay of the conductance, although now in several excited states. Similar results have been obtained for other recently proposed candidates to “anti-Ohmic” wires. These findings open new horizons for possible applications in molecular electronics of these promising systems.