Structures and energetics of Si3N2 clusters

Abstract

Mixed clusters of silicon and nitrogen with formula Si3N2 have been investigated at both SCF and MP2 levels of theory. Of eleven stationary points found below 80 kcal/mol, eight correspond to local minima (LM); of these, five are singlet states. Of the triplets, three LM and one transition state (TS) were characterized. The global minimum corresponds to an angular structure with alternating silicon-nitrogen bonds, in contrast with linear ones for other smaller Si/N clusters. A bipyramidal structure 41.0 kcal/mol high in energy can be seen as a natural pattern for tridimensional growing. In general, structures with more SiN bonds are energetically preferred to those in which the SiSi bonds predominate. Attempts to locate TS correlating with the lowest dissociation channels have been unsuccessful due the complex and computationally demanding search. Despite this fact, the thermodynamic stability for structures I, III, IV, and V is guaranteed, being the energy of the lowest channel a lower bound. The atomization energy for the global minimum structure amounts to 420.6 kcal/mol (MP2).