Ab initio and DFT studies on the structures, binding energies and nature of bonds in X2Y3 metal clusters (X+ = Li+, Na+ and K+; Y-3(2-) = Zn-3(2-), Cd-3(2-) and Hg-3(2-))

作者：Hatami Masoud; Bayat Mehdi^*; Keypour Hassan; Salehzadeh Sadegh

来源：Journal of Theoretical and Computational Chemistry, 2015, 14(6): 1550043.

DOI：10.1142/S0219633615500431

• Ab initio
• binding energy
• nature of bonds
• metal clusters

A comprehensive theoretical study on the structure and stability of linear and triangular isomers of anionic clusters of zinc, cadmium and mercury (Y-3(2-)) and their binding with one and two alkali metal cations (X+ = Li+, Na+, K+) has been investigated at the density functional (BP86 and B3LYP) and ab initio (MP2, MP4 and coupled cluster single and double (CCSD)) methods. The results showed that in all cases, the triangular geometry with D-3h symmetry is more stable than linear one. The calculated values of interaction energies (IE) between Y-3(2-) anions and two X+ cations, Wiberg bond indices (WBI) and the electron densities at bond critical points (BCP), rho(BCP), for Y-X bonds show that among all complexes investigated here at all levels of theory Zn3Li2 and Hg3K2 have the largest and the smallest values of IE, WBI and rho(BCP), respectively. The natural charges of the atoms and WBI involved in the bonding as well as the global value of the charge transfer Delta Q from Y-3(2-) to X+ cation in X2Y3 clusters, evaluated through natural population analysis, confirmed that covalent contribution in Y-X bond formation increases from K+ to Li+. Also the energy decomposition analyses (EDA) were used to detect the nature of interaction in the complexes. The results confirmed that the contribution of electrostatic interactions in present complexes is almost more than 70%.

• 出版日期2015-9