Complexes of XeHXe+ with Simple Ligands: A Theoretical Investigation on (XeHXe+) (L = N2, CO, H2O, NH3)

The structure, stability, and harmonic frequencies of the (XeHXe+L-) complexes (L = N-2, CO, H2O, NH3) were investigated by ab initio and density functional theory (DFT) calculations. Their bonding situation was also assayed by natural bond orbital (NBO), atoms-in-molecules (AIM), and energy decomposition (EDA) analyses. For any L, we located a linear and a T-shaped isomer, whose energy difference progressively increases in the order N-2 < CO < H2O < NH3 and ranges from nearly 0 to 4.5 kcal mol(-1). The absolute complexation energies of both the linear and the T-shaped isomers also increase in the same order, and their EDA analysis revealed the prevailing contribution of electrostatic interactions. The noncovalent character of the bonding between XeHXe+ and L was confirmed by the AIM analysis. In particular, we based our investigation on the joint use of numerical AIM indices and graphic examination of the local Hamiltonian kinetic energy density, K(r). Interestingly, this function visually identifies the covalent regions occupied by XeHXe+ and L and the noncovalent zones existing between them, which include, in particular, the bond critical point located on the Xe-L bond paths. Only for the linear (XeHXe+)NH3 did the AIM analysis suggest an onset of covalency in the xenon-nitrogen interaction. Further work is in progress to examine the effectiveness of K(r), and its plotted forms, as a function of the bonding situation of noble-gas compounds.