Abstract
In this study, we conducted a theoretical simulation to compare the effects of various factors on the atomic and electronic structures and the magnetic properties of copper and gadolinium ions bonded to carboxylated species of (111) diamond surfaces. It was experimentally found that in the temperature range above 120 K, the magnetic moments of chelated Gd3+ and Cu2+ equal 6.73 and 0.981 Bohr magnetons, respectively. In the temperature range from 12 to 2 K, these magnetic moments sharply decrease to 6.38 and 0.88 Bohr magnetons. Specifically, we examined the effects of the number of covalent adatom–diamond substrate bridges, coordination of water molecules, and shallow carbon-inherited spins in the substrate on the physical properties of the metal center. Our simulation predicted that increasing the number of bonds between the chelated metal ion and substrate while decreasing the number of coordinating water molecules corresponded to a decrease in the magnetic moment of metal ions in a metal–diamond system. This is due to the redistribution of the electron charge density in an asymmetric metal–diamond system. By comparing our theoretical results with experimental data, we proposed configurations involving one and, in a minor number of cases, two surface –COO− groups and maximum coordination of water molecules as the most realistic options for Cu- and Gd-complexes.