Spin quenching of transition metals deposited on MgO insulator and CdO semiconductor density functional calculations

We have analyzed spin quenching of first row transition metals deposited on (001) defect‐free and defect‐containing surfaces of MgO insulator and CdO semiconductor by means of density functional calculations and embedded cluster model. Clusters of moderate sizes were embedded in the simulated Coulomb fields that closely approximate the Madelung fields of the host surfaces, and relaxation of ions that surround the defect sites was taken into account. Spin states of metals deposited on the defect free surfaces were maintained as in the isolated metals except for Ti, V, and Co on MgO, and Ti, V, and Cr on CdO. On the defect containing surfaces, spin states were maintained too except for Fe on MgO, and V and Cr on CdO. The metal‐support interactions stabilize the low spin state of the adsorbed metal with respect to the isolated metal, but the effect was not in general enough to quench the spin. Spin polarization effects tend to preserve the spin states of the adsorbed metals relative to those of the isolated metals. Although charge transfer took place from the adsorbed metal to the insulator surface, it took place the other way round from the semiconductor surface to the adsorbed metal. The encountered variations in magnetic properties were attributed to the smaller band gap of the semiconductor, and the behavior of a single metal atom adsorbed on a particular surface was a result of a competition between Hund's rule for the adsorbed metal and the formation of a chemical bond at the interface. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011