The Density Functional Theory Account of Interplaying Long-Range Exchange and Dispersion Effects in Supramolecular Assemblies of Aromatic Hydrocarbons with Spin

• Published in: Molecules (Basel, Switzerland) Switzerland), 2021-12, Vol.27 (1), p.45
• Main Authors: Toader, Ana Maria, Buta, Maria Cristina, Mischie, Alice, Putz, Mihai V, Cimpoesu, Fanica
• Format: Article
• Language: English
• Subjects: Aromatic hydrocarbons; Benchmarks; Benzene; Density functional theory; Hydrocarbons; long-range interactions; Organic compounds; organic radicals; Spintronics
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules27010045

Aromatic hydrocarbons with fused benzene rings and regular triangular shapes, called -triangulenes according to the number of rings on one edge, form groundstates with -1 unpaired spins because of topological reasons. Here, we focus on methodological aspects emerging from the density functional theory (DFT) treatments of dimer models of the = 2 triangulene (called also phenalenyl), observing that it poses interesting new problems to the issue of long-range corrections. Namely, the interaction comprises simultaneous spincoupling and van der Waals effects, i.e., a technical conjuncture not considered explicitly in the benchmarks calibrating long-range corrections for the DFT account of supramolecular systems. The academic side of considering dimer models for calculations and related analysis is well mirrored in experimental aspects, and synthetic literature revealed many compounds consisting of stacked phenalenyl cores, with intriguing properties, assignable to their long-range spin coupling. Thus, one may speculate that a thorough study assessing the performance of state-of-the-art DFT procedures has relevance for potential applications in spintronics based on organic compounds.