Computational study on the electronic g-tensors of hydrophilic and hydrophobic nanodiamonds interacting with water

Hydrogenated and hydroxylated nanodiamonds (NDs) are modeled by putting emphasis on the most common paramagnetic impurities-dangling bonds as well as single substitutional nitrogen atoms-and their interaction with water. It is shown that, despite its overall hydrophobicity, hydrogenated ND can become locally hydrophilic due to the introduced defects; therefore, water molecules may be attracted to the particular sites at its surface. To assess the direct influence of water on the magnetic behavior of NDs, the solvent-induced shift of the g-tensor was employed, indicating that for the same types of impurities, the impact the water has strongly depends on their positions in ND. In addition, water molecules at the locally hydrophilic sites of hydrogenated ND may influence the magnetic behavior of defects to the same extent as it may be influenced in the case of hydroxylated ND. Moreover, the overall hydrophilic nature of the latter does not necessarily guarantee that water, although being strongly attracted to the vicinity of impurity, will form a hydrogen bond network with a substantial impact on the local environment of the unpaired electron. The obtained data imply that in the context of the Overhauser effect, for which the solvent-induced shift of the g-tensor is proposed as a tool to reveal whether some NDs are more favorable for it to occur compared to the others, hydrogenated NDs should perform no worse than hydroxylated ones, despite only the local hydrophilicity of the former.