Semiempirical and ab-initio calculations of clusters: variation of structure and symmetry with size for different compounds

Abstract

Semiempirical (by extended Huckel method) and ab initio RHF SCF calculations are used for the wide range of cluster structures MxXy, where M = Cd,Ag; X = S,I: semiempirical - up to M20X35, and ab initio - for small clusters less than ten atoms. Variation of electronic structure with size for the fragments with tetrahedral coordination (bulklike sphalerite structures) and for some clusters of the lower symmetry allows to predict their possible geometries which are compared with experimental data. The chemical bonding factor (the chemical nature of bounded atoms, coordination number for metal and non-metal atoms, hybridization, etc) is of more importance in properties of the clusters than the familiar quantum confinement effect of semiconductor clusters (like CdS, CdSe, PbS, etc. ). The essential difference in regularities of small cluster formation is analysed for CdS- and AgI- based structures.