Theoretical studies of the structures and properties of (Cl2InN3)n (n = 1–6) clusters

The equilibrium geometries, stabilities, IR spectra, and thermodynamic properties of (Cl 2 InN 3 ) n ( n = 1–6) clusters are systematically investigated at the DFT-B3LYP level. Harmonic vibrational analysis has been performed to assure that the optimized geometries are stable. The optimized results suggest that the core structures of 2 n -membered ring with alternating indium and a-nitrogen atoms are observed in clusters when n ≥ 2. The relative stabilities of (Cl 2 InN 3 ) n ( n = 1–6) clusters were analyzed by means of the dependent relationships between the averaged binding energies, the second-order difference of energies, the HOMO–LUMO energy gaps and the cluster size n , and a local odd-even alternation phenomenon was found. Trends in thermodynamic properties with temperature and oligomerization degree n are discussed, respectively. Thermodynamic analysis of the gas-phase oligomerizations shows that formations of the most stable clusters (Cl 2 InN 3 ) n ( n = 2–6) from the monomer are thermodynamically favorable by the enthalpies and Gibbs free energies in the range of 200–700 K.