Structures, Electronic, and Magnetic Properties of CoK n (n = 2–12) Clusters: A Particle Swarm Optimization Prediction Jointed with First-Principles Investigation.

Transition-metal-doped clusters have long been attracting great attention due to their unique geometries and interesting physical and/or chemical properties. In this paper, the geometries of the lowest- and lower-energy CoK_n (n = 2–12) clusters have been screened out using particle swarm optimization and first principles relaxation. The results show that except for CoK₂ the other CoK_n (n = 3–12) clusters are all three-dimensional structures, and CoK₇ is the transition structure from which the lowest energy structures are cobalt atom-centered cage-like structures. The stability, the electronic structures, and the magnetic properties of CoK_n clusters (n = 2–12) clusters are further investigated using the first principles method. The results show that the medium-sized clusters whose geometries are cage-like structures are more stable than smaller-sized clusters. The electronic configuration of CoK_n clusters could be described as 1S1P1D according to the spherical jellium model. The main components of petal-shaped D molecular orbitals are Co-d and K-s states or Co-d and Co-s states, and the main components of sphere-like S molecular orbitals or spindle-like P molecular orbitals are K-s states or Co-s states. Co atoms give the main contribution to the total magnetic moments, and K atoms can either enhance or attenuate the total magnetic moments. CoK_n (n = 5–8) clusters have relatively large magnetic moments, which has a relation to the strong Co-K bond and the large amount of charge transfer. CoK₄ could be a magnetic superatom with a large magnetic moment of 5 μ_B. [ABSTRACT FROM AUTHOR]