Theory of intermolecular exchange in coupled spin-1/2 nanographenes

Abstract

Open-shell nanographenes can be covalently bonded and still preserve their local moments, forming interacting spins lattices. In the case of benzenoid nanographenes, the Ovchinnikov-Lieb rules anticipate the spin of the ground state of the superstructure, and thereby the sign of the intermolecular exchange. Here we address the underlying microscopic mechanisms for intermolecular exchange in this type of system. We find that, in general, three different mechanisms contribute. First, Hund's ferromagnetic exchange that promotes ferromagnetic interactions of electrons in overlapping orbitals. Second, superexchange driven by intermolecular hybridization, identical to Anderson kinetic exchange, which is a decreasing function of the Hubbard-$U$ energy scale, and is always antiferromagnetic. Third, a Coulomb-driven superexchange, that increases as a function of $U$, and involves virtual excitation of excited molecular orbitals that are extended over the entire structure. We find that Coulomb-driven superexchange can be either ferro or antiferromagnetic, accounting for Ovchinnikov-Lieb rules. We compute these exchange energies for the case of coupled $S=1/2$ phenalenyl triangulenes, using multi-configurational methods both with Hubbard and extended Hubbard models, thereby addressing the influence of long-range Coulomb interactions on the exchange interactions.

arXiv comment14 pages; 10 figures

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• Tuning the Spin Interaction in Non-planar Organic Diradicals Through Mechanical Manipulation
• Conformational tuning of magnetic interactions in coupled nanographenes
• Broken-symmetry magnetic phases in two-dimensional triangulene crystals
• Superexchange Mechanism in Coupled Triangulenes Forming Spin-1 Chains
• On-surface Synthesis of a Ferromagnetic Molecular Spin Trimer
• Magnetic frustration and fractionalization in oligo(indenoindenes)
• A Route Toward the On-Surface Synthesis of Organic Ferromagnetic Quantum Spin Chains
• Spin and Charge Control of Topological End States in Chiral Graphene Nanoribbons on a 2D Ferromagnet
• Two topological phases in exchange alternating spin-1 nanographene chains
• Identification and optimization of accurate spin models for Fermi-Hubbard ladders using matrix product states