New J. Chem., 2016,40, 9060-9072

DOI: 10.1039/C6NJ01334A

Weak interactions within nitryl halide heterodimers

A theoretical study of nitryl halide heterodimers has been carried out using SCS-RI-MP2 and CCSD(T) at the complete basis set (CBS) calculations. For this purpose, 66 heterodimers have been characterized as minima and arranged in six groups depending on the interactions involved and their geometrical arrangements. The CCSD(T)/CBS interaction energies vary between −0.6 and −11.1 kJ mol−1. The heavier the halogen atoms, the larger the interaction energies. Natural bond orbital (NBO) and “atoms-in-molecules” (AIM) theories were then used to analyze the complexes, confirming the presence of halogen, chalcogen, and π-hole interaction bonds. The largest charge-transfer energy contributions were found for halogen bonded complexes (up to 29.1 kJ mol−1). Furthermore, the physical nature of the interactions was studied using symmetry-adapted perturbation theory (SAPT) calculations, and it was concluded that dispersion was the major source of attraction, although electrostatics is important in halogen bonded complexes.

Graphical abstract: Weak interactions within nitryl halide heterodimers