Electron sharing and localization in real space for the Mott transition from 1RDMFT periodic calculations

One-particle reduced density matrix functional theory (1RDMFT) has been applied for the investigation of the real-space picture of the Mott transitions in archetypal hydrogen lattices. The evolution of the degree of electron localization during the transition has been evaluated using electron sharing indices for QTAIM atoms, and the connection between the strength of electronic correlation expressed by the 1RDMFT correlation energy and the degree of electron localization has been analyzed at various stages of transition. The spatial decay of the electron sharing indices in the course of transition has also been evaluated and compared with the results obtained for the Hubbard model and finite cluster calculations

Assessing the reversed exponential decay of the electrical conductance in molecular wires: the undeniable effect of static electron correlation

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.Xunta de Galicia | Ref. GRC2019/24Agencia Estatal de Investigación | Ref. PGC2018-095953-B-I0