From Clusters to Wires - DFT investigations of molybdenum sulfide nanostructures

The dependence of morphology and composition in molybdenum sulfide nanostructures was investigated by density-functional-based calculations. Sulfur-rich compounds preferentially form two-dimensional platelet structures, which can accomodate a large extent of excess sulfur atoms along the platelet edges. Compounds which are understoichiometric in sulfur, i.e., with a negative sulfur extent, contain a metalloid molybdenum core structure, which is stabilised by Mo-Mo metal bonds and decorated by sulfur atoms. Small species of this type are polyhedral clusters, which grow into nanowires with increasing atom number. Close to the bulk stoichiometry of Mo:S = 1:2 larger polyhedral and partially hollow clusters are obtained, which exhibit an octahedral shape at system sizes of up to a few thousands of atoms and finally grow into spherical fullerenes at even larger sizes.