Abstract
We investigate, in the present study, the structural properties, magnetic moments and charge distribution of the solid solution in an immiscible Co–Cu system at equilibrium by first-principles calculation using special quasirandom structures (SQS). In order to mimic the pair and multisite correlation functions of the randomly substitutional fcc solid solutions, the original SQS is developed to include five 16-atom SQS unit cells, i.e., 1/16, 2/16, 3/16, 4/16, and 8/16, enabling to mimic at nine specific alloys compositions. Correspondingly, a new error analysis method is proposed for comparing the situations of various alloy compositions within the SQS unit cells having a same number of atoms. The developed SQS are then applied in the first-principles calculation to study the CoxCu1−x solid solutions (x refers to the Co concentration). It turns out that the calculated results of the lattice constants and magnetic moments versus the Co concentration are in good agreement with the experimental data, and especially, the sharp drop in the magnetic moment near the composition x=0.1 is well reproduced. The heats of formation are also calculated and in good agreement with those obtained from Mediema’s thermodynamic theory and available experimental data. At the alloy compositions x=0.25 and 0.75, some hypothetical crystalline structures of the Co–Cu compounds are respectively calculated and their heats of formation are found to be higher than the solid solution counterparts. Finally, the electron distribution among the atoms in the CoxCu1−x solid solutions is studied and the obtained charge densities show that in the CoxCu1−x solid solutions, the charge distributes mostly between the Co–Co atoms, thus forming attractive covalent bonding.
