Hydrogen-migration governed dynamic magnetic coupling characteristics in nitrogen-vacancy-hydrogen nanodiamonds.

The nitrogen-vacancy center doped with hydrogen (NVH) is one of the most common defects in diamonds, and the doping of hydrogen is known to enable mobility among three equivalent C-radicals in the defect, which noticeably affects the spin coupling among the radicals. Here, we for the first time uncover the dynamic nature of magnetic coupling induced by H-migration in the NVH center of nanodiamonds, using spin-polarized density functional theory calculations and enhanced sampling metadynamics simulations. The mobility of doping H enables the interior NVH region to become a variable magnetic space (antiferromagnetic/AFM versus ferromagnetic/FM). That is, the dynamic H has three frequently reachable binding C sites where H enables the center to exhibit variable AFM coupling (high up to J = -1282 cm-1) and that in other H-reachable regions including N sites, it enables the center to exhibit FM coupling (high up to J = 598 cm-1). The magnetic switching (AFM ↔ FM) and strength fluctuation strongly depend on the H-position which can adjust the ratio of the C radical orbitals in their mixing orbitals for a special three-electron three-center covalent C⋯H⋯C H-bonding and radical orbital distributions. Clearly, this work provides insights into the dynamic switching of magnetic coupling in such multi-radical centers of defect nanodiamonds.