Weak antiferromagnetic coupling in molecular ring is predicted correctly by density functional theory plus Hubbard U

We apply density functional theory with empirical Hubbard U parameter (DFT+U) to study Mn-based molecular magnets. Unlike most previous DFT+U studies, we calibrate U parameters for both metal and ligand atoms using five binuclear manganese complexes as the benchmarks. We note delocalization of the spin density onto acetate ligands due to pi-back bonding, inverting spin polarization of the acetate oxygen atoms relative to that predicted from superexchange mechanism. This inversion may affect the performance of the models that assume strict localization of the spins on magnetic centers for the complexes with bridging acetate ligands. Next, we apply DFT+U methodology to Mn-12 molecular wheel and find antiparallel spin alignment for the weakly interacting fragments Mn-6, in agreement with experimental observations. Using the optimized geometry of the ground spin state instead of less accurate experimental geometry was found to be crucial for this good agreement. The protocol tested in this study can be applied for the rational design of single molecule magnets for molecular spintronics and quantum computing applications