Combined first-principles and thermodynamic approach to M-nitronyl nitroxide (M = Co, Mn) spin helices

The properties of two molecular-based magnetic helices, composed of 3d metal Co and Mn ions bridged by nitronyl nitroxide radicals, are investigated by density-functional calculations. Their peculiar and distinctive magnetic behavior is here elucidated by a thorough description of their magnetic, electronic, and anisotropy properties. Metal ions are antiferromagnetically coupled with the radicals, leading to a ferrimagnetically ordered ground state. A strong metal-radical exchange coupling is found, about 44 and 48 meV for Co and Mn helices, respectively. The latter have also relevant next-nearest-neighbor Mn-Mn antiferromagnetic interactions (of ~6 meV). Co sites are characterized by noncollinear uniaxial anisotropies, whereas Mn sites are rather isotropic. A key result pertains to the Co helix: The microscopic picture resulting from density-functional calculations allows us to propose a spin Hamiltonian of increased complexity with respect to the commonly employed Ising Hamiltonian, suitable for the study of finite-temperature behavior, and that seems to clarify the puzzling scenario of multiple characteristic energy scales observed in experiments.