A density-functional study of the structures and electronic propertiesof neutral, anionic, and endohedrally doped InxPx clusters

摘要

We report extensive ab initio calculations of the structures, binding energies, and magnetic momentsof In_χP_χand In_xP_χ~-clusters(χ=1-15)using a density-functional method that employs linearcombinations of pseudoatomic orbitals as basis sets, nonlocal norm-conserving pseudopotentials,and the generalized gradient approximation for exchange and correlation. Our results, which arecompared with those obtained previously for some of these clusters by means of all-electroncalculations, show that hollow cages with alternating In–P bonds are energetically preferred overother structures for both the neutral and anionic species within the range χ=6-15. We also consider the endohedrally doped X@In_10P_10(X=Cr ,Mn , Fe , Co) and Ti @ In_xP_x(χ=7-12)clusters. Our_l0P_10(X= results show that, except for Ti @ In_7P_7and Ti @ In_8P_8, the transition metal atoms preserve theiratomic spin magnetic moments when encapsulated in the InP cages, instead of suffering either a spincrossover or a spin quenching due to hybridization effects. We also show that the stabilities of someempty and doped InP cages can be explained on the basis of the jellium model.